CN1234796A - Noval substituted naphthopyrans - Google Patents
Noval substituted naphthopyrans Download PDFInfo
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- CN1234796A CN1234796A CN 96180498 CN96180498A CN1234796A CN 1234796 A CN1234796 A CN 1234796A CN 96180498 CN96180498 CN 96180498 CN 96180498 A CN96180498 A CN 96180498A CN 1234796 A CN1234796 A CN 1234796A
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Abstract
Described are novel reversible photochromic 2H-naphtho [1,2-b] pyran compounds, examples of which are compounds having certain substitutents at the number 5 carbon atom of the natphtho portion of the naphthopyran and at the 2-position of the pyran ring. Certain substituents may also be present at the number 6, 7, 8, 9 or 10 carbon atoms of the natphtho portion of the naphthopyran.Also described are organic host materials that contain or that are coated with such compounds. Articles such as ophthalmic lenses or other plastic transparencies that incorporate the novel naphthopyran compounds or combinations thereof with complementary photochromic compounds, e. g., spiro (indoline) type compounds, are also described.
Description
Summary of the invention
The present invention relates to some novel naphthopyran compounds.More specifically say, the present invention relates to new photochromic naphthopyran compounds, and the composition and the goods that comprise these novel naphthopyran compounds.Comprising under the ultraviolet light source irradiation, for example under the uviolizing in being subjected to sunlight or mercury lamp light, the reversible colour-change can take place in many photochromic compounds.When ending uviolizing, this class photochromic compound is got back to its primary colors or colourless state again.
People have synthesized the photochromic compound of number of different types, and are proposed to be used in the application that needs reversible color due to the daylight or deepening.USP 3,567, described a series of pyran derivates among 605 (Becker), comprising some chromene and naphthopyran compounds.These compounds are called chromene derivative, it is reported that colour-change can take place for they, for example be lower than approximately under-30 ℃ the temperature, through uviolizing can from colourless become orange-yellow.Reported also in addition by radiation of visible light or temperature risen to about more than 0 ℃ the time that its color can reversibly be got back to the situation of colourless state again.
USP 5,066, put down in writing in 818 various 3,3-diaryl-3H-naphtho-[2,1-b] pyrylium compound, they have eye (mirror) and the desirable photochromic characteristic in other field, promptly high colour generation and acceptable fadedness.Also disclose 2 of isomery by comparative example's mode in this patent, 2-diaryl-2H-naphtho-[1,2-b] pyrylium compound it is reported that this compounds needs just can fade for a long time after activation.
USP 3,627, described in 690 to comprise small amount of alkali or weak photochromic 2 to middle strong acid, 2-two replacement-2H-naphtho-s [1,2-b] pyrans composition.It is reported that adding acid or alkali can be accelerated the fade rates of the naphthopyran compounds of colour generation in the aphthopyrans composition, thereby they can be applied in eye protection field such as the sun glasses.If wherein also further reported not add above-mentioned additive, fading of 2H-naphtho-[1,2-b] pyrylium compound may need a few hours to return to primary colors fully to many days ability.USP 4,818, disclose in 096 to become blue photochromic chromene or naphthopyran compounds, and wherein the alpha-position at the Sauerstoffatom of pyranoid ring has phenyl group, and the ortho position of this phenyl or contraposition also have nitrogenous substituting group.
The present invention relates to 2H-naphtho-[1, the 2-b] pyrylium compound of new replacement, and beyond thought be to have been found that they except that having overactivity intensity and high colour generation speed, also have the acceptable fade rates.Particularly, in naphthopyran compounds, use some substituting group can add acid on the 5-position of naphtho-part or alkali just can be accelerated fade rates.In addition, these compounds also have some substituting groups on the 2-position of pyranoid ring.Can also there be some substituting groups on 6,7,8,9 or 10 carbon atoms of naphtho-part in the aphthopyrans.
Invent auspicious stating
In recent years, the plastic material that photochromic plastic material, particularly optical field are used, caused that people pay close attention to widely, especially photochromic glass lens is studied, this is that this glass lens has lightweight advantage owing to compare with glass mirror.In addition, because photochromic transparent material can provide the potential security feature, so this transparent use of photochromic material on the vehicles such as automobile and aircraft is also interesting.
According to the present invention, have now found that, can make some and have acceptable fade rates, new 2H-naphtho-[1, the 2-b] pyrylium compound of overactivity intensity and high colour generation speed.These compounds are to have some substituent naphthopyran compounds on naphtho-5 carbon atoms partly in the 2-position of pyranoid ring and aphthopyrans ring, wherein, also can there be some substituting groups on 6,7,8,9 or 10 carbon atoms of naphtho-part in the aphthopyrans ring.These compounds can be represented with following structural formula:
In the structural formula I, R
1Can be group-CH
2X or-C (O) Y, X can be halogen, hydroxyl, benzoyloxy, C
1-C
6Alkoxyl group, C
2-C
6Acyloxy, amino, C
1-C
6List-alkylamino, C
1-C
6Dialkyl amido, i.e. two (C
1-C
6) alkylamino, morpholino, piperidino-(1-position only), 1-indolinyl, pyrrolidyl, trimethylsiloxy, or group-OCH (R
11) Z; Y can be group-OCH (R
11) Z or unsubstituted, mono-substituted or two-replace be selected from following heterocycle: 1-indolinyl, morpholino, piperidino-(1-position only), 1-pyrrolidyl, 1-imidazolidyl, 2-tetrahydroglyoxaline-1-base, pyrazolidyl, pyrazolinyl and 1-piperazinyl; Z is-CN-CF
3, halogen ,-C (O) R
11Or-COOR
11R
11Can be hydrogen or C
1-C
6Alkyl; Described heterocyclic substituting group can C
1-C
6Alkyl or C
1-C
6Alkoxyl group, and halogen wherein can be chlorine or fluorine.
Preferred R
1Be group-CH
2X or-C (O) Y, wherein X is a hydroxyl, C
1-C
4Alkoxyl group, or C
2-C
4Acyloxy, Y are group ,-OCH (R
11) Z, perhaps be the unsubstituted or mono-substituted heterocycle that is selected from 1-indolinyl, morpholino, piperidino-(1-position only) and 1-pyrrolidyl, wherein Z is-CN ,-C (O) R
11, or-COOR
11R
11Be hydrogen or C
1-C
4Alkyl; And the substituting group on the described heterocycle can be C
1-C
4Alkyl or C
1-C
4Alkoxyl group.
More preferably R
1Be group-CH
2X, or-C (O) Y, wherein X is a hydroxyl, C
1-C
4Alkoxyl group, or C
2-C
4Acyloxy, and Y is the unsubstituted or mono-substituted heterocycle that is selected from 1-indolinyl, morpholino and piperidino-(1-position only).R most preferably
1Be methylol, acetoxy-methyl, morpholino carbonyl, or piperidino-(1-position only) carbonyl.
R in the structural formula I
2With each R
3Can be hydrogen, C
1-C
6Alkyl, C
3-C
7Cycloalkyl, unsubstituted, single-, two-or the three-phenyl that replaces, group-OR
6, R wherein
6Can be hydrogen, (C
1-C
6) alkyl, phenyl (C
1-C
3) alkyl, mono-substituted phenyl (C
1-C
3) alkyl, (C
1-C
6) alkoxyl group (C
2-C
4) alkyl, C
3-C
7Cycloalkyl, single (C
1-C
4) C that replaces of alkyl
3-C
7Cycloalkyl, C
1-C
6Haloalkyl, allyl group, group-CH (R
7) W, wherein W can be-CN ,-CF
3, halogen ,-C (O) R
7Or-COOR
7, R wherein
7Can be hydrogen, C
1-C
6Alkyl or (C
1-C
6) alkoxyl group (C
2-C
4) alkyl, perhaps R
6Can be group-C (O) T, wherein T can be hydrogen, C
1-C
6Alkyl, C
1-C
6Alkoxyl group replaces or unsubstituted aromatic yl group phenyl or naphthyl phenoxy group, C
1-C
6Single-or the phenoxy group that replaces of two-alkyl, C
1-C
6Single-or the phenoxy group that replaces of two-alkoxyl group, C
1-C
6Alkyl monosubstituted amino, phenylamino, C
1-C
6Single-or the phenylamino that replaces of two-alkyl, C
1-C
6Single-or the phenylamino that replaces of two-alkoxyl group, the substituting group on the described phenyl or naphthyl respectively is C
1-C
6Alkyl, C
1-C
6Alkoxy or halogen, described halogen or halo substituting group respectively are chlorine or fluorine, and n is selected from integer 0,1,2 and 3.
Preferred R
2With each R
3Be hydrogen, C
1-C
4Alkyl, unsubstituted, single-, two-or the three-phenyl that replaces, group-OR
6, R wherein
6Be C
1-C
4Alkyl or group-CH (R
7) W, wherein W is-COOR
7, and R
7Be hydrogen or C
1-C
4Alkyl, the substituting group on the described phenyl are C
1-C
4Alkyl, C
1-C
4Alkoxyl group or fluorine, and n is selected from integer 0,1 and 2.
More preferably R
2With each R
3Be hydrogen, C
1-C
2Alkyl, unsubstituted, single-, two-or the three-phenyl that replaces, group-OR
6, R wherein
6Be C
1-C
2Alkyl or group-CH (R
7) W, wherein W is-COOR
7, and R
7Be C
1-C
2Alkyl, the substituting group on the described phenyl are C
1-C
2Alkyl, C
1-C
2Alkoxyl group or fluorine, and n is selected from integer 0,1 and 2.R most preferably
2With each R
3Be hydrogen, phenyl, methoxyl group, methyl or fluorine.
In the structural formula I, B and B ' can be selected from separately: (ⅰ) unsubstituted, single-, two-and three-the aromatic yl group phenyl and the naphthyl that replace; (ⅱ) unsubstituted, single-and two-heteroaryl groups pyridyl, furyl, cumarone-2-base, cumarone-3-base, thienyl, thionaphthene-2-base, thionaphthene-3-base, dibenzothiophen base, dibenzofuran base and carbazyl of replacing, wherein said aryl and heterocyclic substituting group are selected from hydroxyl, amino, C
1-C
6Alkyl monosubstituted amino, C
1-C
6Dialkyl amido, morpholino, piperidino-(1-position only), 1-indolinyl, pyrrolidyl, 1-imidazolidyl, 2-tetrahydroglyoxaline-1-base, 2-pyrazolidyl, pyrazolinyl, 1-piperazinyl, C
1-C
6Alkyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, single (C
1-C
6) alkoxyl group (C
1-C
4) alkyl, acryloxy, iso-butylene acyl-oxygen base and halogen, halogen wherein or (halo) base can be fluorine or chlorine; (ⅲ) group shown in following structural formula II A and the II B:
Wherein D can be carbon or oxygen, and E can be the nitrogen of oxygen or replacement, and its condition is that D then is a carbon as E during for the nitrogen that replaces, and the substituting group on the wherein said nitrogen is selected from hydrogen, C
1-C
6Alkyl and C
2-C
6Acyl group; R
8Can be C separately
1-C
6Alkyl, C
1-C
6Alkoxyl group, hydroxyl or halogen, wherein halogen can be chlorine or fluorine; R
9And R
10Hydrogen or C can respectively do for oneself
1-C
6Alkyl; And m can be integer 0,1 or 2; (ⅳ) C
1-C
6Alkyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group (C
1-C
4) alkyl, C
3-C
6Cycloalkyl, single (C
1-C
6) alkoxyl group (C
3-C
6) cycloalkyl, single (C
1-C
6) alkyl (C
3-C
6) cycloalkyl and halo (C
3-C
6) cycloalkyl, described halogen substituting group is a fluorine or chlorine; (ⅴ) group shown in the following structural formula II C:
Wherein U can be hydrogen or C
1-C
4Alkyl, and V can be selected from unsubstituted, single-and two-naphthyl, phenyl, furyl and thienyl of replacing, and wherein said substituting group is C
1-C
4Alkyl, C
1-C
4Alkoxyl group, fluorine or chlorine; Or (ⅵ) B and B ' form unsubstituted, single-or two-fluorenes-9-fork of replacing together or form saturated C
3-C
12Spiral shell-monocyclic hydrocarbon ring, cyclopropylidene for example, inferior cyclobutyl, cyclopentylidene, cyclohexylidene, inferior suberyl, inferior ring octyl group, inferior ring nonyl, inferior ring decyl, ring undecane fork, cyclododecane fork, saturated C
7-C
12Spiral shell-bicyclic hydrocarbon ring pitch as two rings [2.2.1] heptan, promptly inferior norcamphyl, and 1,7,7-trimethylammonium two ring forks in [2.2.1]-heptan, promptly bornenyl, the hot fork of two rings [3.2.1], in two rings [3.3.1] ninth of the ten Heavenly Stems-9-fork, two encircle [4.3.2] undecanes, and saturated C
7-C
12Spiral shell-tricyclic hydrocarbon ring, for example three ring [2.2.1.0
2,6] pitch three ring [5.3.1.1 heptan
2,6] dodecane fork and three ring [3.3.1.1
3,7] last of the ten Heavenly stems fork, promptly inferior adamantyl, wherein the substituting group stuck of fluorenes-9-can be selected from C
1-C
4Alkyl, C
1-C
4Alkoxyl group, fluorine and chlorine.
Preferred B and B ' are selected from separately: (ⅰ) unsubstituted, single-, two-and the three-phenyl that replaces; (ⅱ) unsubstituted, single-and two-heteroaryl groups pyridyl, furyl, cumarone-2-base, cumarone-3-base, thienyl, thionaphthene-2-base, thionaphthene-3-base, dibenzothiophen base, dibenzofuran base and carbazyl of replacing, substituting group on described phenyl and the heterocycle is selected from morpholino separately, piperidino-(1-position only), C
1-C
4Alkyl, C
1-C
4Alkoxyl group and halogen, halogen or (halo) base are fluorine or chlorine; (ⅲ) group shown in the structural formula II A, wherein D is that carbon and E are oxygen; R
8Respectively be C
1-C
4Alkyl, C
1-C
4Alkoxyl group, hydroxyl or halogen, halogen are chlorine or fluorine; R
9And R
10Hydrogen or C respectively do for oneself
1-C
4Alkyl; And m is integer 0,1 or 2; (ⅳ) C
1-C
4Alkyl, C
1-C
6Alkoxyl group (C
1-C
4) alkyl and C
3-C
6Cycloalkyl; (ⅴ) group shown in the structural formula II C, wherein U is hydrogen or methyl, and V is phenyl or list-substituted-phenyl, the substituting group on the described phenyl is C
1-C
4Alkyl, C
1-C
4Alkoxyl group or fluorine; Or (ⅵ) B and B ' form fluorenes-9-fork of unsubstituted or list-replacement together or form together and be selected from following group: saturated C
3-C
8Spiral shell-monocyclic hydrocarbon, saturated C
7-C
10Spiral shell-bicyclic hydrocarbon and saturated C
7-C
10The spiral shell tricyclic hydrocarbon.
More preferably B and B ' are selected from separately: (ⅰ) unsubstituted, single-and two-phenyl of replacing; (ⅱ) unsubstituted, single-and two-heteroaryl groups pyridyl, cumarone-2-base, thionaphthene-2-base of replacing, dibenzothiophen base and dibenzofuran base, the substituting group on described phenyl and the heterocycle is selected from morpholino, piperidino-(1-position only), C
1-C
2Alkyl and C
1-C
2Alkoxyl group; (ⅲ) group shown in the structural formula II A, wherein D is that carbon and E are oxygen; R
8C respectively does for oneself
1-C
2Alkyl, C
1-C
2Alkoxyl group or fluorine; R
9And R
10Hydrogen or C respectively do for oneself
1-C
2Alkyl, and m is integer 0,1 or 2; Or (ⅳ) B and B ' form fluorenes-9-fork together, and be bornenyl, inferior norcamphyl, two rings [3.3.1] ninth of the ten Heavenly Stems-9-fork or inferior adamantyl.B and the B ' phenyl of respectively doing for oneself most preferably, the phenyl that methoxyl group replaces, the phenyl that morpholino replaces, dibenzofuran-2-base or 2,3-Dihydrobenzofuranes-5-base.
Compound can make through the following steps shown in the structural formula I.Benzophenone compound shown in structural formula V and the V A can be buied, and perhaps can utilize the replacement of the Benzoyl chloride suitable replacement shown in the structural formula IV or unsubstituted and commercially available structural formula III or unsubstituted benzene compound to make by Fu-Ke method.Referring to document: Fu-Ke and correlated response thereof; (Grafts andRelated Reactions) George A.Olah; Interscience Publishers; 1964; the 3rd volume; XX XI chapter (synthesizing of aromatic ketone); and Ishihara, people's such as Yugi " 1,2; 3; 4-tetrahydroquinoline and relevant nitrogenous heterocyclic regioselectivity Fu-Ke acylation reaction: ", Englishize association will (J.Chem.Soc.), Perkin Trans.1 to the influence of NH protecting group and ring size; the 3401-3406 page or leaf, 1992.
Compound shown in structural formula III and the IV is dissolved in the kind solvent such as dithiocarbonic anhydride or methylene dichloride, and in the presence of Lewis acid such as aluminum chloride or tin tetrachloride, reaction generates accordingly by the substituted diphenylamine ketone shown in the structural formula V (or the V A among the reaction B).Substituting group on the possible phenyl of R and R ' representative.
Reaction A
In reaction B, make the replacement shown in the structural formula V A or do not replace ketone (wherein B and B ' can represent the group except that replacement or unsubstituted phenyl) and in appropriate solvent such as anhydrous tetrahydro furan (THF), react the corresponding propargyl alcohol shown in the generating structure formula VI with ethinylation sodium.Wherein B and B ' are for replacing or the propargyl alcohol of unsubstituted phenyl can by commercially available ketone or for example to react the ketone that makes by carboxylic acid halides with replacement or unsubstituted benzene, naphthalene or heteroaromatics be feedstock production.Can be by the propargyl alcohol that contains B and B ' group shown in the structural formula II C according to USP5,274,132, described method preparation in hurdle 2, the 40-68 are capable.
Reaction B
Preparing structural formula VIII used in the method for structural formula I aphthopyrans and the naphthols shown in the X III can prepare described in reaction C or D.In reaction C, make 1 shown in the structural formula VII, 4-dihydroxyl-2-naphthoic acid is reacting in appropriate solvent such as anhydrous dimethyl formamide (DMF) with alkylogen (as methyl-iodide) in the presence of the ethyl diisopropylamine, form corresponding 1,4-dihydroxyl-2-2-methyl naphthoate (representing) by the structural formula VIII.Organic chemistry magazine (The Journal of Organic Chemistry), 46 (17), 1981, the 3477 pages are seen in further describing of this reaction.
Reaction C
In reaction D, replacement shown in the formula IX or unsubstituted phenyl methyl ketone, benzophenone or phenyl aldehyde and Succinic acid dimethylester (structural formula X) are reacted in appropriate solvent such as toluene or THF, wherein reaction is to carry out the monoesters of the suitable replacement shown in the generating structure formula XI or α-arylidene succsinic acid having in the presence of alkali such as sodium hydride or the potassium tert.-butoxide.Compound XI and acetic anhydride and anhydrous sodium acetate are together heated, form the acetic ester derivative shown in the corresponding formula XII.Compound XII and spirit of salt and absolute alcohol such as anhydrous methanol one are reacted, generate corresponding by the naphthols shown in the structural formula X III.Further describing of D of reaction seen textbook organic reaction (OrganicReactions), VI volume, the 1st chapter, 1-73 page or leaf, John Wiley; Sons, Inc., New York.
Reaction D
In reaction E, with the propargyl alcohol shown in the structural formula VI and structural formula VIII A (further by (R
3)
nThe VIII that replaces) the naphthols coupling shown in forms the 6-hydroxyl aphthopyrans shown in the structural formula X IV.The 6-hydroxyl substituent of compound shown in the structural formula X IV can pass through for example to react with alkyl halide (as methyl-iodide, iodoethane, bromotoluene etc.) and be converted into the 6-alkoxy base, thereby forms the compound shown in the structural formula X V.In inert solvent such as THF, utilize for example compound shown in lithium aluminum hydride (LAH) the reduction structural formula X V, can produce the compound that the 5-methylol shown in the structural formula X VI replaces.Can utilize the 5-methylol substituting group of compound shown in the whole bag of tricks derivatize structural formula X VI then.For example, 5-methylol substituting group can be converted into alkoxy methyl by making compound shown in the structural formula X VI and alkyl halide (as methyl-iodide, positive propyl bromo, bromotoluene etc.) in that reaction in the presence of alkali such as the salt of wormwood is arranged, thus compound shown in the production X VII.Other method is with the described methylol of carboxylic acid halides (as Acetyl Chloride 98Min., Benzoyl chloride etc.) acidylate, compound shown in the generating structure formula X VIII.In the 3rd example, make described methylol and chlorination trimethyl silyl that reaction in the presence of the acid acceptor (as triethylamine) arranged, thereby produce the trimethyl silyl ether shown in the structural formula X IX.Reaction E
In reaction F, the naphthols shown in propargyl alcohol shown in the coupling structural formula VI and the structural formula X III, the naphthopyran compounds shown in the generating structure formula XX with 6-aryl, 6-alkyl or 6-hydrogen.In inert solvent such as THF, utilize for example compound shown in lithium aluminum hydride (LAH) the reduction structural formula XX, can obtain the 5-methylol compound shown in the formula X XI.Can utilize the 5-methylol substituting group of compound shown in the various different methods derived structure formula X XI then.For example, the 5-methylol can be converted into chloro-methyl group, thereby produce the compound shown in the structural formula X XII by making the reaction of compound shown in the structural formula X XI and thionyl chloride.5-chloromethyl shown in the structural formula X XII in the compound can be further with reaction derivatize as known in the art, for example by make itself and primary, the second month in a season or heterocyclic amine (propylamine for example, diethylamine, morpholine etc.) reaction and obtain the 5-aminomethylation compound shown in the formula XX III.On the other hand, the methylol groups shown in the structural formula X XI in the compound can also react with alkyl halide (as methyl-iodide, propyl iodide, bromotoluene etc.), produces the compound shown in the structural formula XX IV.
Reaction F
The compound that is replaced by amido on the 5-position can prepare by the series reaction shown in the reaction G.Utilization is dissolved in the naphthols shown in the potassium hydroxide water solution structure formula X III in water and the pure mixed solution, the carboxyl naphthols shown in the production XX V.By with excess acetyl chloride, the free hydroxyl group substituting group shown in the protection structural formula XX V in the compound obtains the compound that the acetoxyl group shown in the structural formula XX VI replaces.By reacting, the carboxyl substituent in the formula XX VI compound is converted into acyl chlorides, thereby produces the compound of structural formula XX VII with thionyl chloride.Then by with primary, the second month in a season or heterocyclic amine (as propylamine, diethylamine, morpholine, piperidines etc.) reaction, the acyl chlorides in the formula XX VII compound is converted into amido, thereby obtains compound shown in the structural formula XX VIII.In the presence of HCl, by with methyl alcohol reaction deprotection structural formula XX VIII compound in the acetoxyl group substituting group, produce the naphthol compound shown in the structural formula XX IX.By naphthols shown in the structural formula XX IX and the reaction of the propargyl alcohol shown in the structural formula VI, can make the pyrylium compound that comprises the 5-amido shown in the structural formula XXX again.
Reaction G
Compound shown in the structural formula I can be used for wherein utilizing in the application of organic photochromic material, for example be used for optical mirror slip, ophthalmic lens and plano lens as correct vision, head shield, protective glasses, eye-protection glasses, sun visor, camera gun, window glass, automotive windshield, aircraft and automobile transparent article (as transparent top (T-roofs), side window and rear window), plastic film and plastic plate, fabric and coating (for example coating composition resembles paint), and the verification mark thing on the various safety document (for example need verify or examine bill, passport and driving license).Naphthopyran compounds shown in the structural formula I demonstrate from colourless to yellow to redness/colour-change of purple scope.
The example of desired naphthopyran compounds is as follows in the scope of the invention:
(a) 2,2-two (4-p-methoxy-phenyl)-5-methylol-6-methyl-9-methoxyl group-2H-naphtho-[1,2-b] pyrans;
(b) 2,2-two (4-p-methoxy-phenyl)-5-methylol-6-phenyl-2H-naphtho-[1,2-b] pyrans;
(c) 2,2-two (4-p-methoxy-phenyl)-5-acetoxy-methyl-6-phenyl-2H-naphtho-[1,2-b] pyrans;
(d) 2-(4-p-methoxy-phenyl)-2-(2,3-Dihydrobenzofuranes-5-yl)-5-piperidino-(1-position only) carbonyl-6-methyl-9-methoxyl group-2H-naphtho-[1,2-b] pyrans;
(e) 2,2-two (4-p-methoxy-phenyl)-5-methylol-6-methoxyl group-2H-naphtho-[1,2-b] pyrans;
(f) 2,2-phenylbenzene-5-methoxymethyl-6-methoxyl group-2H-naphtho-[1,2-b] pyrans;
(g) 2,2-spiral shell adamantane subunit-5-acetoxy-methyl-6-methoxyl group-2H-naphtho-[1,2-b] pyrans;
(h) 2,2-two (4-p-methoxy-phenyl)-5-trimethylsiloxy methyl-6-methoxyl group-2H-naphtho-[1,2-b] pyrans;
(i) 2-(4-p-methoxy-phenyl)-2-tertiary butyl-5-methoxymethyl-6-phenyl-9-methoxyl group-2H-naphtho-[1,2-b] pyrans; With
(j) 2-(4-p-methoxy-phenyl)-2-(2,3-Dihydrobenzofuranes-5-yl)-5-chloromethyl-6-methyl-9-methoxyl group-2H-naphtho-[1,2-b] pyrans.
Be not hard to predict, the organic photochromic naphthopyran compounds of structural formula I of the present invention can be used in combination with other suitable complementary organic photochromic material, and they can produce nearly neutral gray or brown color and luster jointly when being subjected to uviolizing to comprise the glass lens of this class photochromic material with box lunch.For example, with can variable color the compound of yellowly become the compound blending of suitable purple with the energy variable color, can produce brown color and luster.Equally, its colour generation attitude is orange compound when producing the grey color and luster when the suitable look compound that turns blue is used in combination.The combination of aforementioned photochromic material also can be used in other Application Areas of non-eye lens.
New naphthopyran compounds of the present invention (for example above-described those) can use separately, also can be used in combination with complementary photochromic compound (photochromic compounds that promptly in about 400-700 nanometer range, has at least one maximum activation absorption peak) or the material that contains them, can also be admixed to by mode such as dissolving or dispersion is used to prepare in the polymer organic substrate material of photochromic article, when being activated to suitable form and aspect (hue), the compound wherein or the mixture of compound are with regard to colour generation.
The complementary organic photochromic material of the first kind that can be used in combination with organic photochromic naphthopyran compounds of the present invention is that (promptly between approximately greater than 570 to 700 nanometers between) has those that maximum activation absorbs in the visible-range greater than 570 nanometers.When being subjected to uviolizing in appropriate solvent or matrix, these materials generally demonstrate blueness, blue-green, or indigo plant-purple color.Many these compounds have been put down in writing in the open source literature.For example, wherein in USP 3,562,172; 3,578,602; Put down in writing spiral shell (indoline) phenoxazine in 4,215,010 and 4,342,668; USP 5,405, put down in writing in 958 on its molecule De phenoxazine part 8 ' and 9 ' position have some substituent spiral shells (indoline) phenoxazine; USP4 has put down in writing spiral shell (indoline) pyrido-benzoxazine in 637,698; USP 4,931, put down in writing spiral shell (benzo indoline) pyrido-benzoxazine and spiral shell (benzo indoline) phenoxazine in 219; Japanese Patent discloses and has put down in writing spiral shell (benzo indoline) aphthopyrans in 62/195383; USP 4,816, disclose spiral shell (indoline) benzoxazine in 584; For example, USP4 discloses spiral shell (indoline) chromene, spiral shell (indoline) aphthopyrans and spiral shell (indoline) quino-pyrans in 880,667; And, put down in writing in 096 and had nitrogenous substituent chromene and aphthopyrans on the pyranoid ring 2-position at USP 4,818.In following textbook, also put down in writing some spiral shells (indoline) pyrylium compound in addition: the technology in the chemistry (Techniques in Chemistry), the III volume, " photochromic ", the 3rd chapter, GlennH.Brown (writing), John Wiley and Sons, Inc., New York, 1971.
The complementary organic photochromic material of second class that can be used in combination with organic photochromic naphthopyran compounds of the present invention is between about 400 be lower than the material that has at least one maximum absorption band in the visible-range of 500 nanometers.When being subjected to uviolizing in appropriate solvent or matrix, these materials generally demonstrate Huang-orange color.This compounds comprises that some chromene is chromene and naphthopyran compounds.Open source literature such as USP 3,567,605; Many these compounds have been put down in writing in 4,826,977 and 5,066,818.The complementary chromene that can be used in combination with naphthopyran compounds of the present invention and other example of aphthopyrans comprise: USP4 has those of spiral shell diamantane group on the alpha-position of its pyranoid ring Sauerstoffatom described in 826,977; Have some substituent naphtho-s-[1 on 5 and 6 carbon atoms of the naphtho-of aphthopyrans part and on 2 of pyrans, 2-b] pyrylium compound, it is 08/164,187 the common theme that does not cut off U.S. Patent application that these compounds have constituted the application number of submitting on December 9th, 1993; USP 5,066, have the substituent 3H-naphtho-of at least one ortho position substituted-phenyl [2,1-b] pyrylium compound on its pyranoid ring 3-position described in 818; Wherein at the 3H-naphtho-[2 that has some substituting group on 8 carbon atoms and on 7 or 9 carbon atoms, have some substituting group (all these substituting groups all are positioned at the naphtho-part of aphthopyrans), 1-b] pyrylium compound, these compounds have constituted the theme that the application number of submitting on June 21st, 1993 is 08/080,246 common not exhausted U.S. Patent application; USP 5,384, and the 3-position of its pyranoid ring described in 077 is by (ⅰ) aryl substituent and (ⅱ) 3H-naphtho-[2, the 1-b] pyrans that replaces of phenyl substituent, and wherein said phenyl substituent has on 3 and 4 carbon atoms and its condensed 5-or 6-unit heterocycle; Has the g that condenses in aphthopyrans, i, or the replacement on l limit or unsubstituted 5 or 6 yuan of heterocyclic diaryl-3H-naphtho-s [2,1-b] pyrylium compound, these compounds have constituted the theme that the application number of submitting on April 8th, 1994 is 08/225,022 common not exhausted U.S. Patent application; USP 5,238, described the naphthopyran compounds that is replaced by for example methoxyl group on 8 carbon atoms of naphtho-part in the aphthopyrans ring in 931; USP 5,274, described naphthopyran compounds in 132, and the example has 3-aryl-3-aromatic yl alkenyl naphthopyran compounds; And naphtho-[2, the 1-b] pyrylium compound that on its 5 carbon atoms, is replaced by for example acetoxyl group, these compounds have constituted USP 5,244,602 theme.
The complementary organic photochromic material of the 3rd class that can be used in combination with organic photochromic naphthopyran compounds of the present invention is to have maximum absorption and at those materials that also have another maximum absorption in the visible-range of about 700 nanometers of about 500-in the visible-range of about 500 nanometers of about 400-.When being subjected to uviolizing in appropriate solvent or the matrix, these materials generally demonstrate from yellow to purple and Huang/and brown to purple/gray colour-change.These examples for compounds comprise 2H-phenanthro-[4, the 3-b] pyrans of some replacement; 3H-phenanthro-[1, the 2-b] pyrans that replaces; And benzopyran compounds, for example have those of substituting group and replacement or unsubstituted heterocycle (for example condensing thionaphthene or cumarone ring on the benzo of chromene part) on the 2-position of pyranoid ring.Described this compounds in back is common not exhausted U.S. Patent application 08/286,039 and the USP5 that submitted on August 4th, 1994,411,679 theme.
If desired or require, photochromic article of the present invention can comprise the mixture of a kind of photochromic compound or multiple photochromic compound.The mixture of single photochromic compound or photochromic compound can be used for obtaining some and activates look such as neutral gray or brown.
The compounds of this invention (below be also referred to as and be included into the second class photochromic compound) can also with the as herein described first complementary class photochromic compound (can variable color for blue, blue-green, or the compound of indigo plant-purple) the organic photochromic material or be used in combination with other organic photochromic material in aforementioned second photochromicization of the class thing.Arbitrary compounds in the mixture of the first kind or the second class photochromic compound or these compounds can be separately or they can demonstrate from yellow to purple and Huang/brown the 3rd class photochromic material to purple/gray colour-change is used in combination with as herein described together.
The usage quantity of each photochromic material as herein described (or usage ratio) should be able to make the organic substrate material that applies or be mixed with the mixture of described photochromic compound or described compound demonstrate required color, for example show basic neutral color when the sunlight with filtered activates, promptly the activatory photochromic compound can provide as far as possible near the neutral color.
The neutral gray color is demonstrating the absorption that is equal to relatively in the visible-range of 400 to 700 nanometers.And neutral brown color demonstrates the absorption intensity in the 400-550 nanometer range wherein to a certain extent greater than the spectrum of absorption intensity in the 550-700 nanometer range.The another kind of method of describing color is according to its tristimulus coordinates, and except that its luminance factor was its colourity, it had also described chromaticity.In the CIE system, tristimulus coordinates obtains by the ratio of asking tristimulus value and its summation, i.e. x=X/ (X+Y+Z) and y=Y/ (X+Y+Z).Color described in the CIE system can be marked and drawed in chromaticity diagram, is generally the curve of tristimulus coordinates x and y.Referring to F.W.Billmeyer, the 47-52 page or leaf (second edition) of the multi color technics principle of Jr. and Max Saltzman (Principles of Color Technology) book, John Wiley and Sons, N.Y. (1981)." near neutral color " used herein be meant its activate with solar light irradiation (Air Mass 1 or 2) 40% optical transmittance afterwards chromaticity coordinate value " x " and " y " have the color of following value range (D5 irradiating source): x=0.260-0.400, y=0.280-0.400.
Coating or the amount that is admixed to the photochromic material in the substrate material or contains their composition are not key, as long as institute's consumption can produce the photochromic effect that naked eyes can be distinguished when excited state.Usually this amount is called photochromic amount.Desirable colour intensity and mix or apply the used method of photochromic material when concrete consumption depends on irradiation usually.In general, the amount coated or photochromic material that mixes is many more, and colouring intensity is just tetanic to certain limit more.
The relative consumption of above-mentioned photochromicization thing is variable, and depends in part on the relative intensity and the final required color of color of the excited state material of these compounds.In general, mix or be coated in photochromic optical substrate material (on) photochromic material total amount can approximately 0.05-be about 1.0 for every square centimeter of surface that is mixed with or is coated with photochromic material, as 0.1 to about 0.45 milligram.When using the mixture of above-mentioned complementary class organic photochromic material, the weight ratio of these materials, i.e. (weight ratio of the first kind and the second class material), (weight ratio of second class and the 3rd class material) and (weight ratio of aphthopyrans of the present invention and other second compounds) will be about 1: about 3: 1 of 3-, for example about 0.75: 1-changes between about 2: 1.The first kind, second class, and the complementary combination of compounds of the described organic photochromic of the 3rd class can have at about 1: 3: 1-3: the weight ratio that changes between 1: 3.
Photochromic material of the present invention can adopt the various different methods coatings described in this area or be incorporated in substrate material such as the organic polymer substrate material.These methods comprise and photochromic material is dissolved in or is distributed in the substrate material, for example by the mode that before polymerization photochromic material is joined in the monomer substrate material it are distributed in wherein appropriate location; By shifting in the hot solution that substrate material is immersed in photochromic material or by heat photochromic material is drawn in the substrate material; Photochromic material is distributed between the adjacent layer of substrate material as one deck independently, for example as the part of polymeric film; And the coating photochromic material makes its top coat part as substrate material.Term " suction " is meant and comprises following situation: photochromic material is penetrated into separately in the substrate material, and solvent assists in the transfer photochromic material in porous polymer, gas phase transfer and other this metastasis.
For medically reason or in order to follow the fashion, can apply (chemical aspect and color aspect) compatible color matching thing (tints) on substrate material is dyestuff, to obtain more perfect effect.The concrete dyestuff of selecting changes according to the result of above-mentioned requirements and desire acquisition.In one embodiment, can select the dyestuff with the complementary colors of excited state photochromic material, for example, to obtain more neutral color or to absorb the specific wavelength incident light.In another embodiment, selected dyestuff is at photochromic material and can be substrate material under the disactivation attitude situation required tone is provided.
In photochromic material coating or before being incorporated in the substrate material, simultaneously or can also in substrate material, mix subsidiary material afterwards.For example, before being coated to substrate material, UV light absorber can be mixed with photochromic material earlier, perhaps this class absorption agent is superposeed for example superimposed stratification between photochromic material and incident light.In addition, also can before it is coated to substrate material, stablizer be mixed with photochromic material, to improve the fast light fatigability of photochromic material.The stablizer of being considered has: as hindered amine (hindered amine) photostabilizer and singlet oxygen quencher (as with organic ligand coordinate nickel ion).They can use separately, also can be used in combination.These stablizers are recorded in USP 4,720, in 356.At last, can also be in the surface applied of substrate material suitable protective coating.They can be wear resistnat paint and/or the coating that is used as oxygen barrier layers.These coating are as known in the art.
Substrate material is normally transparent, but also can be translucent or even opaque.Substrate material only need be to the electromagnetic spectrum part (can produce ultraviolet (UV) the light wavelength part of opening state (open form) material) that activates photochromic material and comprise that the visible spectrum of the maximum absorption wavelength of UV activated form (promptly opening type) material partly is transparent getting final product.Preferably, the color of substrate material can not be covered the color of activation form photochromic material, that is change in color is very tangible for observing.More preferably, the substrate material goods are solid transparent or optically transparent material, the material that for example is fit to optical application, for example plane mirror and glasses, the window material, the transparent part of the vehicles (as the wind shelves), the transparency on the aircraft (aircraft transparencies), plastic plate, polymeric film etc.
The example of the polymer organic substrate material that can together use with photochromic material as herein described or composition comprises: polymkeric substance, it is following monomeric homopolymer and multipolymer: polyvalent alcohol (allyl carbonate) monomer [polyol (allyl carbonate) monomers], the diethylene glycol dimethacrylate monomer, the triacrylate monomer of the acrylate monomer of diisopropenyl benzene monomer and alkoxylated polyol such as ethoxylated trimethylolpropane; Polyfunctional monomer is promptly single-, two-, three-, four-or the polymkeric substance of polyfunctional acrylate and/or methacrylate monomer, i.e. homopolymer and multipolymer, polyacrylic ester, polymethacrylate, poly-(methacrylic acid C
1-C
12Alkyl ester) as polymethylmethacrylate, poly-(methacrylic ester of oxyalkylene) is as poly-(polyethylene glycol dimethacrylate), poly-(methacrylic ester of alkoxylate phenol) is as poly-(the diisobutylene acid esters of ethoxylation dihydroxyphenyl propane), rhodia, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene dichloride, urethane, thermoplastic poly carbonic ether, polyester, polyethylene terephthalate, polystyrene, poly-(alpha-methyl styrene), styrene-methylmethacrylate copolymer, styrene-acrylonitrile copolymer, polyvinyl butyral acetal, and the polymkeric substance of two allylidene tetramethylolmethanes (diallylidenepentaerythritol), be homopolymer and multipolymer, particularly with polyvalent alcohol (allyl carbonate) monomer, for example multipolymer of glycol ether diallyl carbonic ether and acrylate monomer.
The blend of transparent copolymer and transparent polymer also is suitable for use as substrate material.Preferred substrate material is by following polymer optical clear organic polymer materials: thermoplastic polycarbonate resin, and as the carbonic ether cross-linked resin derived from the dihydroxyphenyl propane photoreactive gas, it is sold with the LEXAN trade(brand)name; Polyester is as the material of selling with trade(brand)name MYLAR; Polymethylmethacrylate is as the material of commodity PLEXIGLAS by name; Polyvalent alcohol (allyl carbonate) monomer, especially the polymkeric substance of glycol ether two (allyl carbonates) (this monomer is sold with the CR-39 trade(brand)name), and polyvalent alcohol (allyl carbonate) is as the multipolymer of diethylene glycol bis-allyl carbonate and other copolymerisable monomer, as with the multipolymer of vinyl-acetic ester, for example by 80-90% diethylene glycol bis-allyl carbonate and 10-20% vinyl-acetic ester, the multipolymer that forms by described diene propyl carbonate of 80-85% and 15-20% vinyl-acetic ester particularly, and the multipolymer that forms with urethane with terminal diacrylate functional group, as USP 4,360,653 and 4,994, described in 208; And contain the multipolymer of the aliphatic urethane of allyl group or acrylyl functional group with terminal portions, as USP 5,200, described in 483; Polyvinyl acetate, polyvinyl butyral acetal, urethane, following polymer of monomers: glycol ether diisobutylene acid esters monomer, the Viscoat 295 of diisopropenyl benzene monomer and ethoxylation; Rhodia, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, the multipolymer of polystyrene and vinylbenzene and methyl methacrylate, vinyl-acetic ester and vinyl cyanide.More specifically say, estimate that photochromatic benzopyran compound of the present invention can use with the organic optical resin monomer that is used to produce the optical clear polymkeric substance, for example wherein said polymkeric substance is meant the material that is fit to optical application, for example plane mirror and eye-use lens, window is with the transparency of material and used for vehicle.This optical clear polymkeric substance can have the refractive index of about 1.48-about 1.75 (as about 1.495-about 1.66).
The present invention more elaborates with the following example, but these embodiment only are illustrative, all is conspicuous because carry out various modifications for those skilled in the art and change.
Embodiment 1
Step 1
In reaction flask, with 4,4 '-dimethoxy benzophenone (0.27 mole) is dissolved in the saturated 200ml anhydrous tetrahydro furan of acetylene, and at room temperature stirs.In reaction flask, add the dimethylbenzene/mineral oil suspension (0.3 mole of sodium carbide) of 18% (weight percent) sodium carbide, and stir the mixture.Under the room temperature, in nitrogen atmosphere, stir after 16 hours, the content of reaction flask mixture is added in the mixture of 5% (weight) hydrochloric acid and ice.The miscellany extracted with diethyl ether of gained is separated organic layer, and washing is through anhydrous sodium sulfate drying.Solvent removed in vacuo ether and tetrahydrofuran (THF) obtain comprising 1, and the oily product of 1-two (4-p-methoxy-phenyl)-2-propine-1-alcohol, this product need not to be further purified and be directly used in down in the step.
Step 2
With 1 of step 1,1-two (4-p-methoxy-phenyl)-2-propine-1-alcohol (about 0.025 mole) and 4-hydroxyl-6-methoxyl group-1-methyl-2-2-methyl naphthoate (5g, 0.022 mole) are added to and comprise in the 200ml reaction of toluene flask, and stir.Add catalytic amount right-toluenesulphonic acids (about 100 milligrams), stirred the mixture 4 hours.Then reaction mixture is poured in 10% weight sodium hydroxide solution.Separate organic layer, washing, and use anhydrous sodium sulfate drying.Vacuum is removed residual solvent toluene.Utilize silicagel column and chloroform: the mixture of hexane=1: 3 is an eluent, purifying gained oily matter.Merge the photochromic compound fraction, vacuum is removed eluent.Induce products therefrom crystallization from hexane.Reclaim product and have 132-133 ℃ of fusing point.NMR (Nuclear Magnetic Resonance) spectrum shows the structure and 2 of this product, 2-two (4-p-methoxy-phenyl)-5-methoxycarbonyl-6-methyl-9-methoxyl group-2H-naphtho-[1,2-b] pyrans unanimity.
Step 3
With 2 of step 2 gained, 2-two (4-p-methoxy-phenyl)-5-methoxycarbonyl-6-methyl-9-methoxyl group-[2H]-naphtho-[1,2-b] pyrans (1.7g, 0.0034 mole) is dissolved in the reaction flask that comprises the 200ml tetrahydrofuran (THF), and stirs.Carefully add lithium aluminum hydride (0.13g, 0.0034 mole) then, at room temperature stirred the mixture 2 hours.Add the 2-propyl alcohol, the hydrochloric acid soln of adding 5% weight that continues.With methylene dichloride (2 * 100ml) extract the gained mixtures, merge organic extracting solution, after dried over mgso, the solvent removed in vacuo methylene dichloride.Induce products therefrom crystallization from ether, and collect formed crystal by suction filtration.The fusing point that reclaims product (1.0g) is 125-127 ℃.NMR (Nuclear Magnetic Resonance) spectrum shows the structure and 2 of products therefrom, 2-two (4-p-methoxy-phenyl)-5-methylol-6-methyl-9-methoxyl group-2H-naphtho-[1,2-b] pyrans unanimity.
Embodiment 2
Step 1
In comprising 200 milliliters of (ml) reaction of toluene flasks, add potassium tert.-butoxide (75 grams (g), 0.75 mole).Heating gained pulpous state liquid added the mixture of benzophenone (91g, 0.5 mole), Succinic acid dimethylester (90g, 0.62 mole) and toluene (100g) to reflux temperature under the nitrogen atmosphere in about 30 minutes.After adding, under reflux temperature, keep the gained pasty mixture 2 hours, be cooled to room temperature then.Add about 400ml water, stirred formed mixture 30 minutes.Separate water layer, use the dilute hydrochloric acid acidifying, use the 200ml methylbenzene extraction again.Solvent removed in vacuo obtains a viscosity oily matter, with after fixing, wherein comprises product 4,4-phenylbenzene-3-methoxycarbonyl-3-butenoic acid.This product needn't be further purified and be directly used in down in the step.
Step 2
The product of step 1 is dissolved in contains in the 200ml reaction of toluene flask.Add acetic anhydride (100g) and anhydrous sodium acetate (15g) in reaction flask, this mixture 17 hours refluxes.Cool off the gained mixture then to room temperature, solvent removed in vacuo.In the reaction flask that comprises the gained residue, add methylene dichloride (200ml), add 200ml water again, then slowly add solid sodium carbonate, till no carbonic acid gas is overflowed.The separate dichloromethane layer, washing, and solvent removed in vacuo obtains a viscosity oily matter that comprises 1-acetoxy-3-methoxycarbonyl-4-phenylnaphthalene.
Step 3
In the reaction flask of the 1-acetoxy-3-methoxycarbonyl that comprises step 2-4-phenylnaphthalene, add methyl alcohol (400ml).In reaction flask, add concentrated hydrochloric acid (2ml) subsequently again, and heating gained mixture is to reflux temperature.After 4 hours, cooling mixture is to room temperature, solvent removed in vacuo, and suction filtration is collected the gained crystal, and uses methanol wash crystals collected, dry air then.The product that is recovered to (100g) has 174-176 ℃ of fusing point.NMR (Nuclear Magnetic Resonance) spectrum (NMR) shows that the structure of products therefrom is consistent with 4-phenyl-3-methoxycarbonyl-1-naphthols.
Step 4
In comprising 100ml reaction of toluene flask, add step 3 gained 4-phenyl-3-methoxycarbonyl-1-naphthols (2g) and by the step 1 among the embodiment 1 obtain 1,1-two (4-p-methoxy-phenyl)-2-propine-1-alcohol (2g), and stirring.Heating gained mixture to 40 ℃.Add catalytic amount (several) Witco 1298 Soft Acid (promptly being enough in mixture, produce the amount of dark red color).After 3 hours, cooling mixture is washed 40 ℃ of stirrings.Separate organic layer then, solvent removed in vacuo toluene.Utilize silicagel column and hexane: the mixture of ethyl acetate=2: 1 is an eluent purifying gained oily matter.Collect the photochromic compound fraction, solvent removed in vacuo.With hexane-ether crystalline mixture products therefrom (2.0g), suction filtration is collected and is obtained the canescence crystal.The fusing point that reclaims product is 168-169 ℃.NMR (Nuclear Magnetic Resonance) spectrum (NMR) shows the structure and 2 of products therefrom, 2-two (4-p-methoxy-phenyl)-5-methoxycarbonyl-6-phenyl-2H-naphtho-[1,2-b] pyrans unanimity.
Step 5
With 2 of step 4 gained, 2-two (4-p-methoxy-phenyl)-5-methoxycarbonyl-6-phenyl-2H-naphtho-[1,2-b] pyrans (10.0g, 0.02 mole) is dissolved in the reaction flask that contains the 300ml tetrahydrofuran (THF).Stir down the careful lithium aluminum hydride (1.2g, 0.032 mole) that adds in this solution, heated mixt to 40 ℃ reaction 2-1/2 hour.Behind the cool to room temperature, add the 2-propyl alcohol, adding 5% (weight) aqueous hydrochloric acid that continues.(3 * 100ml) extract the gained mixture with ether.Merge organic extracting solution and use dried over mgso.The solvent removed in vacuo ether.Induce the crystallization from ether of gained residue, and suction filtration is collected crystal.Be recovered to the required product of 3 grams.NMR (Nuclear Magnetic Resonance) spectrum (NMR) shows the structure and 2 of products therefrom, 2-two (4-p-methoxy-phenyl)-5-methylol-6-phenyl-2H-naphtho-[1,2-b] pyrans unanimity.
Embodiment 3
With 2 of step 4 gained among the embodiment 2,2-two (4-p-methoxy-phenyl)-5-methylol-6-phenyl-2H-naphtho-[1,2-b] pyrans (2.0g, 0.004 mole) is dissolved in the reaction flask that contains 200ml methylene dichloride and 1.2 equivalent triethylamines.Stir down, in mixture, added Acetyl Chloride 98Min. (0.37g, 0.0048 mole) and reflux 4 hours.After being cooled to room temperature, add ether, filtering by-product hydrochloric acid triethylamine.By silicagel column purifying products therefrom, use chloroform as eluent.Collect the photochromic compound fraction, solvent removed in vacuo.Induce and reclaim product (0.2g) crystallization from ether.Nucleus magnetic resonance (NMR) spectrum shows the structure and 2 of products therefrom, 2-two (4-p-methoxy-phenyl)-5-acetoxy-methyl-6-phenyl-2H-naphtho-[1,2-b] pyrans unanimity.
Embodiment 4
Step 1
Comprise potassium hydroxide (25g), adding 3-methoxycarbonyl-4-methyl-7-methoxyl group-1-naphthols (12g) in the reaction flask of water (250ml) and ethanol (50ml).Heated mixt is 6 hours in vapor bath, and cool to room temperature is poured into mixture in excessive cold rare (about 5% weight) hydrochloric acid.The separating obtained solid product of suction filtration obtains the required product 3-carboxyl of 11g-4-methyl-7-methoxyl group-1-naphthols after the drying.
Step 2
3-carboxyl-4-methyl-7-methoxyl group-1-the naphthols (11g) that in the reaction flask that comprises the 100ml methylene dichloride, adds step 1 gained.Stir and add triethylamine (10g, 0.1 mole) down.The formed thermopositive reaction mixture of cooling in ice bath.Holding temperature is 5 ℃, simultaneously dripping acetyl chloride (4g, 0.05 mole).In 5 ℃ of following restir mixtures 15 minutes, be warming up to room temperature then, further stirred 15 minutes, be poured into subsequently in excessive cold rare (about 5% weight) aqueous hydrochloric acid.Suction filtration goes out precipitated product from this two-phase mixture, with the fresh methylene chloride washing, obtains the required product of 11g after the drying.NMR spectrum shows that the structure of products therefrom is consistent with 1-acetoxy-3-carboxyl-4-methyl-7-methoxynaphthalene.
Step 3
1-acetoxy-3-carboxyl-4-methyl-7-the methoxynaphthalene (11g) that in the reaction flask that comprises the 20ml thionyl chloride, adds step 2, this mixture of heating in vapor bath.After about 30 minutes, when no longer including the HCl effusion, utilize rotatory evaporator to remove excessive thionyl chloride, obtain the acyl chlorides solid.Products therefrom 1-acetoxy-3-chloroformyl-4-methyl-7-methoxynaphthalene need not to be further purified and is directly used in down in the step.
Step 4
One half point short run of the 1-acetoxy-3-chloroformyl-4-methyl-7-methoxynaphthalene of step 3 gained is joined in the reaction flask that comprises methylene dichloride (50ml), piperidines (4.25g, 0.05 mole) and triethylamine (5g, 0.05 mole) mixture.After adding, add excessive cold dilute hydrochloric acid (the about 5% weight) aqueous solution, and mix gained solution.Separate organic layer, water, the dilute sodium carbonate aqueous solution and water washing successively.The solvent removed in vacuo methylene dichloride obtains required product, is an oily matter.NMR spectrum shows that the structure of products therefrom is consistent with 1-acetoxy-3-piperidino-(1-position only) carbonyl-4-methyl-7-methoxynaphthalene.
Step 5
The mixture that in the reaction flask of the 1-acetoxy-3 that comprises step 4-piperidino-(1-position only) carbonyl-4-methyl-7-methoxynaphthalene, adds (200ml) methyl alcohol and concentrated hydrochloric acid (2ml).The formed reaction mixture of backflow is 2 hours in vapor bath.Cooling mixture is poured in the diluted hydrochloric acid aqueous solution to room temperature then.The formed throw out of suction filtration, washing, drying obtains the required product of 4.8g, is the brown crystal.NMR spectrum shows that the structure of products therefrom is consistent with 3-piperidino-(1-position only) carbonyl-4-methyl-7-methoxyl group-1-naphthols.
Step 6
In containing 100ml reaction of toluene flask, add the 3-piperidino-(1-position only) carbonyl-4-methyl-7-methoxyl group-1-naphthols (2.5g) and 1-(2,3-Dihydrobenzofuranes-5-yl)-1-(4-the p-methoxy-phenyl)-2-propine-1-alcohol (2.5g) of step 5, and stir.Stir down, heated mixt to 50 ℃ adds several Witco 1298 Soft Acids (being enough to produce wine-colored amount).After 2 hours, reaction mixture adds entry to room temperature.The washing organic layer, and remove with rotatory evaporator and to desolvate.Utilize the hexane of silicagel column and 1: 1: ethyl acetate mixture is an eluent purifying gained oily matter.Merge the fraction contain photochromic compound, concentrate the back and at a small amount of ether: induced crystallization in the hexanes mixtures.Suction filtration reclaims required product, obtains the 2.6g crystal after the drying, and fusing point is 201-203 ℃.NMR spectrum shows structure and 2-(4-p-methoxy-phenyl)-2-(2,3-Dihydrobenzofuranes-5-yl)-5-piperidino-(1-position only) carbonyl-6-methyl-9-methoxyl group-2H-naphtho-[1,2-b] pyrans unanimity of products therefrom.
Embodiment 5
The A part
Test the photochromatic benzopyran compound that is incorporated in the polymer samples according to following method.Containing 50 grams by 4 parts of ethoxylation dihydroxyphenyl propane diisobutylene acid esters (BPA 2EO DMA), 2,2 of 1 part of Polyethylene Glycol-600 diisobutylene acid esters and 0.033% (weight percent) '-flask of the grams of monomer blend that azo two (2-methyl propionitrile) (AIBN) constitutes in the adding volumetric molar concentration be 1.5 * 10
-3Aphthopyrans.By stirring, mild heat is dissolved in the grams of monomer blend naphthopyran compounds in case of necessity.After obtaining clear solution, it is poured in the dull and stereotyped mold that interior dimensions is inch (15.24cm) * 6,2.2mm * 6 inch (15.24cm).The sealing mold and is placed in the horizontal airflow, and setting program control baking oven rose to 95 ℃ from 40 ℃ at 5 hours at interval, 95 ℃ of maintenances 3 hours, reduced temperature to 60 ℃ maintenance at least 2 hours then, finished bake cycle then.After opening mold, utilize diamond blade that polymer flake is cut into 2 inches (5.1 centimetres) test square.
The B part
The photochromic speed of response of the made photochromic test square of test A part on optical bench.Before testing on the optical bench, earlier photochromic test square was shone about 15 minutes with 365 nanometer ultraviolet rays, to activate photochromic compound, place then to keep about 15 minutes in 76 ℃ of baking ovens with (bleach) or the inactivation photochromic compound of fading.The refrigeration test square exposed to the open air 2 hours under room fluorescent lights to room temperature at least then, hid at least 2 hours thereafter, tested on temperature remains the optical bench of 75 (23.9 ℃) subsequently.150 watts of xenon arc lamps of configuration on optical bench, Remote dimmer (shutter) is bathed as the copper sulfate of above-mentioned arc lamp scatterer; Can remove the Schott WG-320nm edge filter of short wavelength's ray; Neutral density filter and can insert the specimen holder that is tried square.The collimated light beam that will be sent by tungsten lamp is to pass through square with the almost orthogonal angle of square.After square, the suitable optical filter (photopic filter) of control tungsten lamp light by being connected with detector.Suitable optical filter sees through wavelength makes detector imitate the reaction of human eye, and handles the output signal of detector by radiometer.
The changing value of optical density(OD) (Δ OD) is pressed described recording: the test square of the attitude of will fading (bleachedstate) is inserted on the specimen holder, adjust transmissivity and reach 100%, open the xenon lamp dimmer and carry out uviolizing, make the test square fade to activation (being deepening) attitude from the attitude of fading, measure the transmissivity of activated state, and calculate the optical density(OD) changing value according to formula Δ OD=log (100/%Ta), and wherein %Ta represents the percentage transmittance under the excited state, and logarithm is to be the truth of a matter with 10.
Δ OD/Min represents photochromic compound to ultraviolet reaction sensitivity, under uviolizing, measures in the first five (5) second time, and be basic representation then with the per minute.The measuring method of saturated light density value (OD) is identical with the measuring condition of Δ OD/Min, and just the embodiment compound in the his-and-hers watches 1 carries out uviolizing 20 minutes continuously.The λ that is reported in the table 1
MaxVisible spectrum wavelength during activation (colour generation) the body generation maximum absorption of the photochromic compound in two (allyl carbonate) compositions of expression glycol ether.Fade rates (T1/2) is meant to be removed after the activating light source, and the absorption of the activated state of the naphthopyran compounds of test in the square at room temperature (75,23.9 ℃) reaches required timed interval of a half of maximum absorption, is unit representation with the second.The tabulation of the test result of each compound is in table 1 among the embodiment.
Table 1 embodiment λ
MaxΔ OD/Min Δ OD@ fade rates compound, (visible light) sensitivity is saturated, (T1/2) 1 520 0.38 0.42 303sec, 2 506 0.32 0.26 149sec, 3 508 0.33 0.25 109sec, 4 535 0.34 0.65＞800sec
Table 1 is the result show, 2H-naphtho-[1, the 2-b] fade rates of pyrylium compound is subjected to the property effect of 5-bit substituent significantly.For example, compound 1-3 has acceptable bleaching speed (being fade rates), and fading of compound 4 is just very slow.All these 4 embodiment compounds all have high OD value (being intensity of activation) and high colour generation speed (being sensitivity) under saturated situation.
Although the present invention describes in detail by the particular content of particular, these detailed contents must not take and limit the scope of the present invention to have only the included content of additional claim just to be scope of the present invention as.
Claims (20)
1. the naphthopyran compounds shown in the following structural formula:
Wherein:
(a) R
1Be selected from group-CH
2X or-C (O) Y, wherein X is a halogen, hydroxyl, benzoyloxy, C
1-C
6Alkoxyl group, C
2-C
6Acyloxy, amino, C
1-C
6List-alkylamino, C
1-C
6Dialkyl amido, morpholino, piperidino-(1-position only), 1-indolinyl, pyrrolidyl, trimethylsiloxy, or group-OCH (R
11) Z, Y is group-OCH (R
11) Z or unsubstituted, mono-substituted or two-replace be selected from following heterocycle: the 1-indolinyl, morpholino, piperidino-(1-position only), the 1-pyrrolidyl, the 1-imidazolidyl, 2-tetrahydroglyoxaline-1-base, pyrazolidyl, pyrazolinyl and 1-piperazinyl, wherein Z is-CN ,-CF
3, halogen ,-C (O) R
11Or-COOR
11, R
11Be hydrogen or C
1-C
6Alkyl; Substituting group on the described heterocycle is selected from C
1-C
6Alkyl and C
1-C
6Alkoxyl group, and described halogen is meant chlorine or fluorine;
(b) R
2With each R
3Be hydrogen, C
1-C
6Alkyl, C
3-C
7Cycloalkyl, unsubstituted, single-, two-or the three-phenyl that replaces, group-OR
6, R wherein
6Be hydrogen, (C
1-C
6) alkyl, phenyl (C
1-C
3) alkyl, list-substituted-phenyl (C
1-C
3) alkyl, (C
1-C
6) alkoxyl group (C
2-C
4) alkyl, C
3-C
7Cycloalkyl, single (C
1-C
4) C that replaces of alkyl
3-C
7Cycloalkyl, C
1-C
6Haloalkyl, allyl group, group-CH (R
7) W, wherein W is-CN ,-CF
3, halogen ,-C (O) R
7Or-COOR
7, R wherein
7Be hydrogen, C
1-C
6Alkyl or (C
1-C
6) alkoxyl group (C
2-C
4) alkyl, perhaps R
6Be group-C (O) T, wherein T is a hydrogen, C
1-C
6Alkyl, C
1-C
6Alkoxyl group replaces or unsubstituted aromatic yl group phenyl or naphthyl phenoxy group, C
1-C
6Single-or the phenoxy group that replaces of two-alkyl, C
1-C
6Single-or the phenoxy group that replaces of two-alkoxyl group, C
1-C
6Alkyl monosubstituted amino, phenylamino, C
1-C
6Single-or the phenylamino that replaces of two-alkyl, C
1-C
6Single-or the phenylamino that replaces of two-alkoxyl group, each substituting group on the described phenyl or naphthyl is C
1-C
6Alkyl, C
1-C
6Alkoxy or halogen, described halogen or halo substituting group respectively do for oneself chlorine or fluorine, and n is selected from integer 0,1,2 and 3; With
(c) B and B ' are selected from separately:
(ⅰ) unsubstituted, single-, two-and three-the aromatic yl group phenyl and the naphthyl that replace;
(ⅱ) unsubstituted, single-and two-heteroaryl groups pyridyl, furyl, cumarone-2-base, cumarone-3-base, thienyl, thionaphthene-2-base, thionaphthene-3-base, dibenzothiophen base, dibenzofuran base and carbazyl of replacing, substituting group on described aryl and the heterocycle is selected from hydroxyl, amino, C
1-C
6Alkyl monosubstituted amino, C
1-C
6Dialkyl amido, morpholino, piperidino-(1-position only), 1-indolinyl, pyrrolidyl, 1-imidazolidyl, 2-tetrahydroglyoxaline-1-base, 2-pyrazolidyl, pyrazolinyl, 1-piperazinyl, C
1-C
6Alkyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, single (C
1-C
6) alkoxyl group (C
1-C
4) alkyl, acryloxy, iso-butylene acyl-oxygen base and halogen, described halogen or (halo) base are meant fluorine or chlorine;
(ⅲ) group shown in the following structural formula:
Wherein D is carbon or oxygen, and E is the nitrogen of oxygen or replacement, and its condition is that D then is a carbon as E during for the nitrogen that replaces, and the substituting group on the wherein said nitrogen is selected from hydrogen, C
1-C
6Alkyl and C
2-C
6Acyl group; Each R
8Be C
1-C
6Alkyl, C
1-C
6Alkoxyl group, hydroxyl, chlorine or fluorine; R
9And R
10Respectively be hydrogen or C
1-C
6Alkyl; And m is integer 0,1 or 2;
(ⅳ) C
1-C
6Alkyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group (C
1-C
4) alkyl, C
3-C
6Cycloalkyl, single (C
1-C
6) alkoxyl group (C
3-C
6) cycloalkyl, single (C
1-C
6) alkyl (C
3-C
6) cycloalkyl and halo (C
3-C
6) cycloalkyl, described halogeno-group is a fluorine or chlorine; With
(ⅴ) group shown in the following structural formula:
Wherein U is hydrogen or C
1-C
4Alkyl, and V is selected from unsubstituted, single-and two-naphthyl, phenyl, furyl and thienyl of replacing, and wherein said substituting group is C
1-C
4Alkyl, C
1-C
4Alkoxyl group, fluorine or chlorine; Or
(ⅵ) B and B ' form unsubstituted, single-or two-fluorenes-9-fork of replacing together or form saturated C
3-C
12Spiral shell-monocyclic hydrocarbon ring, saturated C
7-C
12Spiral shell-bicyclic hydrocarbon ring and saturated C
7-C
12Spiral shell-tricyclic hydrocarbon ring, the substituting group that wherein said fluorenes-9-sticks is selected from C
2-C
4Alkyl, C
1-C
4Alkoxyl group, fluorine and chlorine.
2. the naphthopyran compounds of claim 1, wherein:
(a) R
1Be selected from group-CH
2X and-C (O) Y, wherein X is a hydroxyl, C
1-C
4Alkoxyl group, or C
2-C
4Acyloxy, Y are group-OCH (R
11) the unsubstituted or mono-substituted heterocycle that is selected from 1-indolinyl, morpholino, piperidino-(1-position only) and 1-pyrrolidyl of Z, wherein Z is-CN ,-C (O) R
11Or-COOR
11R
11Be hydrogen or C
1-C
4Alkyl; And the substituting group on the described heterocycle is selected from C
1-C
4Alkyl and C
1-C
4Alkoxyl group;
(b) R
2With each R
3Be hydrogen, C
1-C
4Alkyl, unsubstituted, single-, two-or the three-phenyl that replaces, group-OR
6, R wherein
6Be C
1-C
4Alkyl or group-CH (R
7) W, wherein W is-COOR
7, and R
7Be hydrogen or C
1-C
4Alkyl, the substituting group on the described phenyl are C
1-C
4Alkyl, C
1-C
4Alkoxyl group or fluorine, and n is selected from integer 0,1 and 2; With
(c) B and B ' are selected from separately:
(ⅰ) unsubstituted, single-, two-and the three-phenyl that replaces;
(ⅱ) unsubstituted, single-and two-heteroaryl pyridyl, furyl, cumarone-2-base, cumarone-3-base, thienyl, thionaphthene-2-base, thionaphthene-3-base, dibenzothiophen base, dibenzofuran base and carbazyl of replacing, substituting group on described phenyl and the heterocycle is selected from morpholino separately, piperidino-(1-position only), C
1-C
4Alkyl, C
1-C
4Alkoxyl group and halogen, described halogen or (halo) base are fluorine or chlorine;
(ⅲ) group shown in the following structural formula:
Wherein D is that carbon and E are oxygen; R
8C respectively does for oneself
1-C
4Alkyl, C
1-C
4Alkoxyl group, hydroxyl or halogen, described halogen are chlorine or fluorine; R
9And R
10Hydrogen or C respectively do for oneself
1-C
4Alkyl; And m is integer 0,1 or 2;
(ⅳ) C
1-C
4Alkyl, C
1-C
6Alkoxyl group (C
1-C
4) alkyl and C
3-C
6Cycloalkyl; With
(ⅴ) group shown in the following structural formula:
Wherein U is hydrogen or methyl, and V is the phenyl of phenyl or list-replacement, and the substituting group on the described phenyl is C
1-C
4Alkyl, C
1-C
4Alkoxyl group or fluorine; Or
(ⅵ) B and B ' form the fluorenes-9-fork of unsubstituted or list-replacement together or form together and be selected from following group: saturated C
3-C
8Spiral shell-monocyclic hydrocarbon ring, saturated C
7-C
10Spiral shell-bicyclic hydrocarbon ring and saturated C
7-C
10Spiral shell tricyclic hydrocarbon ring.
3. the naphthopyran compounds of claim 2, wherein:
(a) R
1Be group-CH
2X or-C (O) Y, wherein X is a hydroxyl, C
1-C
4Alkoxyl group or C
2-C
4Acyloxy, and Y is the unsubstituted or mono-substituted heterocycle that is selected from 1-indolinyl, morpholino and piperidino-(1-position only);
(b) R
2With each R
3Be hydrogen, C
1-C
2Alkyl, unsubstituted, single-, two-or the three-phenyl that replaces, group-OR
6, R wherein
6Be C
1-C
2Alkyl or group-CH (R
7) W, wherein W is-COOR
7, and R
7Be C
1-C
2Alkyl, the substituting group on the described phenyl are C
1-C
2Alkyl, C
1-C
2Alkoxyl group or fluorine, and n is selected from integer 0,1 and 2; With
(c) B and B ' respectively are selected from:
(ⅰ) unsubstituted, single-and two-phenyl of replacing;
(ⅱ) unsubstituted, single-and two-heteroaryl pyridyl, cumarone-2-base, thionaphthene-2-base of replacing, dibenzothiophen base and dibenzofuran base, each substituting group on described phenyl and the heterocycle is selected from morpholino, piperidino-(1-position only), C
1-C
2Alkyl and C
1-C
2Alkoxyl group; With
(ⅲ) group shown in the following structural formula:
Wherein D is that carbon and E are oxygen; R
8C respectively does for oneself
1-C
2Alkyl, C
1-C
2Alkoxyl group or fluorine; R
9And R
10Hydrogen or C respectively do for oneself
1-C
2Alkyl, and m is integer 0,1 or 2; Or
(ⅳ) B and B ' form fluorenes-9-fork together, and be bornenyl, inferior norcamphyl, two rings [3.3.1] ninth of the ten Heavenly Stems-9-fork or inferior adamantyl.
4. the naphthopyran compounds of claim 3, wherein R
1Be methylol, acetoxy-methyl, morpholino carbonyl or piperidino-(1-position only) carbonyl; R
2With each R
3Be hydrogen, phenyl, methoxyl group, methyl or fluorine; And B and the B ' phenyl of respectively doing for oneself, the phenyl that methoxyl group replaces, the phenyl that morpholino replaces, dibenzofuran-2-base or 2,3-Dihydrobenzofuranes-5-base.
5. be selected from following naphthopyran compounds:
(a) 2,2-two (4-p-methoxy-phenyl)-5-methylol-6-methyl-9-methoxyl group-2H-naphtho-[1,2-b] pyrans;
(b) 2,2-two (4-p-methoxy-phenyl)-5-methylol-6-phenyl-2H-naphtho-[1,2-b] pyrans;
(c) 2,2-two (4-p-methoxy-phenyl)-5-acetoxy-methyl-6-phenyl-2H-naphtho-[1,2-b] pyrans;
(d) 2-(4-p-methoxy-phenyl)-2-(2,3-Dihydrobenzofuranes-5-yl)-5-piperidino-(1-position only) carbonyl-6-methyl-9-methoxyl group-2H-naphtho-[1,2-b] pyrans;
(e) 2,2-two (4-p-methoxy-phenyl)-5-methylol-6-methoxyl group-2H-naphtho-[1,2-b] pyrans;
(f) 2,2-phenylbenzene-5-methoxymethyl-6-methoxyl group-2H-naphtho-[1,2-b] pyrans;
(g) 2,2-spiral shell adamantane subunit-5-acetoxy-methyl-6-methoxyl group-2H-naphtho-[1,2-b] pyrans;
(h) 2,2-two (4-p-methoxy-phenyl)-5-trimethylsiloxy methyl-6-methoxyl group-2H-naphtho-[1,2-b] pyrans;
(i) 2-(4-p-methoxy-phenyl)-2-tertiary butyl-5-methoxymethyl-6-phenyl-9-methoxyl group-2H-naphtho-[1,2-b] pyrans; With
(j) 2-(4-p-methoxy-phenyl)-2-(2,3-Dihydrobenzofuranes-5-yl)-5-chloromethyl-6-methyl-9-methoxyl group-2H-naphtho-[1,2-b] pyrans.
6. photochromic article is comprising the naphthopyran compounds of the claim 1 of polymer organic substrate material and photochromic amount.
7. the photochromic article of claim 6, wherein polymer organic substrate material is selected from polyacrylic ester, polymethacrylate, poly-(methacrylic acid C
1-C
12Alkyl ester), poly-(methacrylic ester of oxyalkylene), poly-(methacrylic ester of alkoxylate phenol), rhodia, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene dichloride, thermoplastic poly carbonic ether, polyester, urethane, polyethylene terephthalate, polystyrene, poly-(alpha-methyl styrene), styrene-methylmethacrylate copolymer, styrene-acrylonitrile copolymer, polyvinyl butyral acetal and following polymer of monomers: polyvalent alcohol (allyl carbonate) monomer, the polyfunctional acrylic ester monomer, multifunctional methacrylate monomer, diethylene glycol dimethacrylate monomer, diisopropenyl benzene monomer, the acrylate monomer of alkoxylated polyol and two allylidene tetramethylolmethane monomers.
8. photochromic article is comprising the naphthopyran compounds of the claim 2 of polymer organic substrate material and photochromic amount.
9. the photochromic article of claim 8, wherein polymer organic substrate material is selected from polyacrylic ester, polymethacrylate, poly-(methacrylic acid C
1-C
12Alkyl ester), poly-(methacrylic ester of oxyalkylene), poly-(methacrylic ester of alkoxylate phenol), rhodia, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene dichloride, thermoplastic poly carbonic ether, polyester, urethane, polyethylene terephthalate, polystyrene, poly-(alpha-methyl styrene), styrene-methylmethacrylate copolymer, styrene-acrylonitrile copolymer, polyvinyl butyral acetal and following polymer of monomers: polyvalent alcohol (allyl carbonate) monomer, the polyfunctional acrylic ester monomer, multifunctional methacrylate monomer, diethylene glycol dimethacrylate monomer, diisopropenyl benzene monomer, the acrylate monomer of alkoxylated polyol and two allylidene tetramethylolmethane monomers.
10. the photochromic article of claim 9, wherein polymer organic substrate material is to be selected from following solid transparent homopolymer or multipolymer: polymethylmethacrylate, poly-methacrylate second diester, poly-(the diisobutylene acid esters of ethoxylation dihydroxyphenyl propane), thermoplastic poly carbonic ether, polyvinyl acetate, polyvinyl butyral acetal, urethane and following polymer of monomers: diethylene glycol bis-allyl carbonate monomer, diethylene glycol dimethacrylate monomer, diisopropenyl benzene monomer and ethoxylated trimethylolpropane triacrylate monomer.
11. wherein in the organic substrate material surface that every square centimeter was mixed with or was coated with photochromic material, there is about 0.05-1.0 milligram photochromic compound in the photochromic article of claim 10.
12. the photochromic article of claim 11, wherein said goods are eyeglass.
13. photochromic article, comprising the naphthopyran compounds of the claim 3 of photochromic amount be selected from following polymer organic substrate material: polymethylmethacrylate, poly-methacrylate glycol ester, poly-(the diisobutylene acid esters of ethoxylation dihydroxyphenyl propane), thermoplastic poly carbonic ether, polyvinyl acetate, polyvinyl butyral acetal, urethane and following polymer of monomers: diethylene glycol bis-allyl carbonate monomer, diethylene glycol dimethacrylate monomer, diisopropenyl benzene monomer and ethoxylated trimethylolpropane triacrylate monomer.
14. photochromic article, comprising the naphthopyran compounds of the claim 4 of photochromic amount be selected from following polymer organic substrate material: polymethylmethacrylate, poly-methacrylate glycol ester, poly-(the diisobutylene acid esters of ethoxylation dihydroxyphenyl propane), thermoplastic poly carbonic ether, polyvinyl acetate, polyvinyl butyral acetal, urethane and following polymer of monomers: diethylene glycol bis-allyl carbonate monomer, diethylene glycol dimethacrylate monomer, diisopropenyl benzene monomer and ethoxylated trimethylolpropane triacrylate monomer.
15. photochromic article, it comprises the polymer organic substrate material of solid transparent, and the naphthopyran compounds of (a) at least a claim 1 of photochromic amount and (b) at least aly approximately have other photochromic compounds that at least one maximum activation absorbs in the 400-700 nanometer range.
16. the photochromic article of claim 15, polymer organic substrate material wherein is selected from polyacrylic ester, polymethacrylate, poly-(methacrylic acid C
1-C
12Alkyl ester), poly-(methacrylic ester of oxyalkylene), poly-(methacrylic ester of alkoxylate phenol), rhodia, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene dichloride, thermoplastic poly carbonic ether, polyester, urethane, polyethylene terephthalate, polystyrene, poly-(alpha-methyl styrene), styrene-methylmethacrylate copolymer, styrene-acrylonitrile copolymer, polyvinyl butyral acetal and following polymer of monomers: polyvalent alcohol (allyl carbonate) monomer, the polyfunctional acrylic ester monomer, multifunctional methacrylate monomer, diethylene glycol dimethacrylate monomer, diisopropenyl benzene monomer, the acrylate monomer of alkoxylated polyol and two allylidene tetramethylolmethane monomers.
17. the photochromic article of claim 15, photochromic compounds wherein (b) is selected from:
(a) at the about 400 organic photochromic materials that have at least one maximum absorption to the visible-range that is lower than 500 nanometers;
(b) in the visible-range of about about 500 nanometers of 400-, have maximum absorption, and the organic photochromic material that in the visible-range of about about 700 nanometers of 500-, also has maximum absorption; With
(c) in visible-range, has the organic photochromic material that maximum activation absorbs greater than 570 nanometers; With
(d) mixture of described organic photochromic material.
18. the photochromic article of claim 17, photochromic compounds wherein (b) is for having the organic photochromic material that maximum activation absorbs in the visible-range greater than 570 nanometers.
19. the photochromic article of claim 16, wherein polymer organic substrate material is to be selected from following solid transparent homopolymer or multipolymer: polymethylmethacrylate, poly-methacrylate glycol ester, poly-(the diisobutylene acid esters of ethoxylation dihydroxyphenyl propane), thermoplastic poly carbonic ether, polyvinyl acetate, polyvinyl butyral acetal, urethane and following polymer of monomers: diethylene glycol bis-allyl carbonate monomer, diethylene glycol dimethacrylate monomer, diisopropenyl benzene monomer and ethoxylated trimethylolpropane triacrylate monomer.
20. the photochromic article of claim 17, photochromic compounds wherein (b) is selected from: spiral shell (indoline) phenoxazine, spiral shell (indoline) pyrido-benzoxazine, spiral shell (benzo indoline) pyrido-benzoxazine, spiral shell (benzo indoline) phenoxazine, spiral shell (benzo indoline) aphthopyrans, spiral shell (indoline) benzoxazine, spiral shell (indoline) chromene, spiral shell (indoline) aphthopyrans, spiral shell (indoline) quino-pyrans, spiral shell (indoline) pyrans, 3H-naphtho-[2,1-b] pyrans, 2H-phenanthro-[4,3-b] pyrans; 3H-phenanthro-[1,2-b] pyrans, the mixture of benzopyran compounds and these photochromic compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96180498 CN1234796A (en) | 1996-10-02 | 1996-10-02 | Noval substituted naphthopyrans |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96180498 CN1234796A (en) | 1996-10-02 | 1996-10-02 | Noval substituted naphthopyrans |
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| Publication Number | Publication Date |
|---|---|
| CN1234796A true CN1234796A (en) | 1999-11-10 |
Family
ID=5127931
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|---|---|---|---|
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|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974002A (en) * | 2010-10-21 | 2011-02-16 | 华东理工大学 | Naphthapyran derivative containing sulfonamide groups |
| CN109593196A (en) * | 2014-05-07 | 2019-04-09 | 三菱瓦斯化学株式会社 | The resin and resin combination manufactured using polycondensation |
| CN111116541A (en) * | 2020-01-19 | 2020-05-08 | 浙江大学宁波理工学院 | Photochromic fluorine-containing naphthopyran compound |
-
1996
- 1996-10-02 CN CN 96180498 patent/CN1234796A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974002A (en) * | 2010-10-21 | 2011-02-16 | 华东理工大学 | Naphthapyran derivative containing sulfonamide groups |
| CN101974002B (en) * | 2010-10-21 | 2012-07-18 | 华东理工大学 | Naphthapyran derivative containing sulfonamide groups |
| CN109593196A (en) * | 2014-05-07 | 2019-04-09 | 三菱瓦斯化学株式会社 | The resin and resin combination manufactured using polycondensation |
| CN109593196B (en) * | 2014-05-07 | 2021-08-13 | 三菱瓦斯化学株式会社 | Resin produced by polycondensation and resin composition |
| CN111116541A (en) * | 2020-01-19 | 2020-05-08 | 浙江大学宁波理工学院 | Photochromic fluorine-containing naphthopyran compound |
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| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: PPG INDUSTRIES INC. TO: PPG IND OHIO INC. |
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| CP03 | Change of name, title or address |
Address after: American Ohio Applicant after: PPG Industries, Inc. Address before: American Pennsylvania Applicant before: PPG Industries Inc. |
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |