TW411362B - Naphthopyrans and photochromic articles - Google Patents

Abstract

Described are novel reversible photochromic 2H-naphtho[1,2-b]pyran compounds, examples of which are compounds having certain substituents at the number 5 carbon atom of the naphtho 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 naphtho 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

8 & Η · 24 Amendment No. 85113915 Chinese Application-Zoritzmin * lattice, τ hundred, year I] pp Five 'invention description () 4 group, Ci-C: 4-alkoxy or CyC: 4- Benzyloxy and Y are unsubstituted, monosubstituted heterocyclic rings (selected from the group consisting of p-indolyl, morpholino, and piperidinyl) ^ The best case is: R 丨 is hydroxymethyl, ethoxy Fluorenyl, morpholinocarbonyl or piperidinyl. Min 2 and each R_3 in formula I may be hydrogen, C6 C6_alkyl 'C3_C7_cycloalkyl, unsubstituted, mono-, di-, or tri-substituted phenyl, · 〇r6 group ( Where Re can be hydrogen, (crC6) alkyl, benzyl (c〗 _c3) alkyl, mono-substituted phenyl (CrC3) alkyl ′ (C 丨 -C6) alkoxy (c2-C4) alkane Group, 匸 3-(: 7cycloalkyl, crC6 卣 alkyl, allyl'_ch (r7) w group (wherein W can be -CN, -CF3 '), and R7 can be Hydrogen, C 丨 -C6 · alkyl or (C 丨-(: 6) alkoxy (c2-c4) alkyl) 'or' foot 6 may be -C (0) T group (where τ may be Hydrogen, Cj · c0-alkyl, C {-Cg-alkoxy, substituted or unsubstituted aryl'phenyl or fluorenyl, phenoxy, Ci-C: 6 via mono- or di-alkane Group substituted phenoxy, c 1-C: 6. Very mono- or di-alkoxy substituted phenoxy, the phenyl or fluorenyl substituent is C "C0 alkyl 'CrC: 6 alkoxy Or halo, each of the halogen or halo substituents is gas or fluorine, and η is an integer selected from 0, 1, 2, and 3. It is preferred that the rule 2 and each be hydrogen, C丨 -c4-alkyl, not taken Substituted, mono-, di- or tri-substituted phenyl, _〇R6 group (where ~ is Crc4), or -CH (R7) W group (where W is -COOR7, where R " (7 疋 wind or 匚 1-〇4- 丨)) The substituent is C, C4, C4-C4, alkoxy or fluoro'η is an integer selected from 0, 1, and 2. This paper Standards apply to Chinese national standards (CNS > A4 specifications (2IOX 297 mm) (please read the notes on the back before filling out this page) Order the Central Consumers Bureau of the Ministry of Economic Affairs, the Consumer Cooperative Cooperative Imprint 4113b 411362 at B7 V. Invention Note (1) (Please read the notes on the back before filling out this page} The present invention is about some novel lyan compounds. More specifically, the present invention is about novel photochromic compounds and compounds containing This new piperan compound object. When exposed to light containing ultraviolet rays (such as: ultraviolet light in the light or light from a lamp), many photochromic compounds will produce reversible color changes When UV light is discontinuous, such photochromic compounds will return to their original color or colorless state. Various types of photochromic compounds have been synthesized and recommended for applications in which sunlight induces reversible color changes, or for applications where darkening is desired. U_S. Patent 3,567,605 (Becker) describes a series of pyran derivatives, Includes certain benzo 11 pyrans and sulfans. These compounds are derivatives of chromene, which change their color due to exposure to ultraviolet light at temperatures below about -3 ° C (eg, from colorless to yellow Clear color). The report states that the compounds can return to a colorless state by irradiating the compound with visible light or increasing its temperature above 0 ° C. 11.8. 316 valence 5,066,818 describes various 3,3-diaryl-31 {-蓁 [2,1-b] pyrans have photochromic properties desired for eyeglass lenses and other applications, that is, high discoloration and can be Accepted discoloration. It is also mentioned in the comparative example of US Patent 5,066,818 that the heterogeneous 2,2-diaryl-2 Η- 荇 [1,2-b] pyridine printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs must not be printed. Discoloration does not occur until a long period of activation is accepted. U.S. Patent 3,627,690 describes a 2,2-disubstituted-2H-naphthalene [l, 2-b] pyran composition containing a minor amount of a base or a weak to medium strength acid. It has been reported that the addition of an acid or hydrazone to various sulfan compositions to increase the discoloration rate of pigmented piperans, thereby making them useful for eye protection applications such as sunglasses. It is also reported that the paper size without the aforementioned additives is applicable to the Chinese National Standard (tNS) A4 specification (2 丨 0X297 mm) 411362 A7 B7 Printed by the staff of the Central Bureau of Standards of the Ministry of Economic Affairs. Du V. Invention Description (2H- ^ [l, 2-b] p The ratio of fading to lan is several hours to several days to completely fade. U. s. Patent 4,818,096 describes a blue light-sensitive color-changing benzene or sulfonation, which is used in onan There is a phenyl group at the ubiquitous position of the ring oxygen, and a nitrogen-containing substituent at the ortho or para position. The present invention is unexpectedly discovered about a novel substituted 2H- 荇 [1,2-b] pyran compound It has an acceptable rate of fading, high activation strength and same color rate. In particular, it makes some substituents at the 5-position of the pu part of the tea compound, which can be improved without the addition of acid or test Fade, color rate. In addition, these compounds have some substituents at the 2 · position of the onan ring. There can also be some on the 6, 7, 8, 9, or 10 carbon atoms of the fluorene moiety of tea Substituents are present.

In recent years, 'photochromic plastic materials (especially plastic materials for optical applications) have been valued. In particular, since the photochromic plastic lens is lighter than the glass lens', research has been conducted on the photochromic plastic lens. In addition, 'I am also interested in light-transparent, transparent materials for vehicles such as cars and airplanes, because such materials have a safer nature. D According to the present invention, it has now been found that it is possible to make certain materials with acceptable thumb color rates. A novel pyran compound with high activation strength and high coloring rate. These compounds can be thought of as sulfanilone, which has two substituents at the 2-position of the sulfaned ring and the 5th carbon atom of the fluorene moiety. There may also be some substituents on the 6, 7, 8, 9, or 10 atoms of the hydrazone portion of piran. These compounds can be represented by the following general formula: _i ·-I I ^ ϋ.--* * (Please read the notes on the back before filling this page) -5- 41136. A7 B7 V. Description of the invention (3)

In the general formula I printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, R 1 may be a -CH2X group or a -C (0) Y group, where X may be halogen, hydroxyl, benzyloxy, or c i- Cf alkoxy, c 2-c6-fluorenyloxy, amine, CrC6--alkylamino, crc6-dialkylamino (ie, bis (C i-C6) amino) Lindy, Ludian, 1- 丨 1 * Domanyl, p-pyrrolyl, trimethylsiloxy or -OCHdDZ; Y can be -OCH (Ru) Z group or unsubstituted, via Mono- or di-substituted heterocycles (selected from 1- 啕 p-Domanyl, morpholino, brityl, 1-p-pyridyl, 1-imidyl, 2-weiyelin-1-yl , P is sulphur, p is yalyl, and 1-olfactory); Z is -CN, -CF3, quotient, -C (0) R12 or -COOR13; Ru and R12 can be hydrogen or C Group: R 13 may be hydrogen; this heterocyclic substituent may be <: 丨-(: 6-alkoxy or (: 1-(: 6-alkoxy, halogen may be gas or fluorine.), Preferably The case is: RiS-CI ^ X or -C (0) Y group, where X is hydroxyl, CrCf alkoxy or c2-c4-fluorenyloxy, γ is -ociKRdZ group or unsubstituted, via Single replacement or double take Substituted heterocycles (selected from 1-pyridyl, morpholino, stilbene, and 1- < »p p groups), where Z is -CN, -C (0) R12 or -COOR13 Ru and R12 are hydrogen or CfCV alkyl; r13 is hydrogen; heterocyclic substituent is CrCf alkyl or crc4-alkoxy. More preferably: 1 ^ is-(: 112 or -C (0) Y group, where X is hydroxyl-6- This paper size is applicable to Chinese National Standard (CNS) A4 specifications (2) ο X 2ί > 7 mm) _ „-------- 装-事- .- (Please read the note on the back ^! ^ Before filling out this page} -'V0 8 & Η · 24 Amendment No. 85113915 Chinese Application-Zoe Lizmin * Grid, τ100, Year I] pp 5 'Explanation of the invention () 4 group, Ci-C: 4-alkoxy or CyC: 4-fluorenyloxy, Y is an unsubstituted, mono-substituted heterocyclic ring (selected from the group consisting of 4 indolyl, morpholino And piperidinyl). The best case is: R is hydroxymethyl, ethoxymethyl, morpholinocarbonyl, or piperidinyl. Min 2 and each R_3 in formula I may be hydrogen. , C plant C6_alkyl 'C3_C7_cycloalkyl, unsubstituted, mono-, di- or tri-substituted phenyl, · 〇r6 group (where Re can be hydrogen, (crC 6) Alkyl, stupid (c〗 _c3) alkyl, mono-substituted phenyl (CrC3) alkyl ′ (C 丨 -C6) alkoxy (c2-C4) alkyl, fluorene 3-(: 7 Cycloalkyl, c rC6 alkyl, allyl'_ch (r7) w group (wherein W can be -CN, -CF3 'youxin, where R7 can be hydrogen, C 丨 -C6 · alkane Or (C 丨-(: 6) alkoxy (c2-c4) alkyl) 'or' foot 6 can be -C (0) T radical (where τ can be hydrogen, Cj · c0-alkyl , C {-Cg-alkoxy, substituted or unsubstituted aryl'phenyl or fluorenyl, phenoxy, Ci-C: 6 mono- or di-, alkyl-substituted phenoxy, c 1-C: 6. Very mono- or di-alkoxy substituted phenoxy, the phenyl or fluorenyl substituent is C "C0 alkyl 'CrC: 6 alkoxy or halide, the halogen or Each of the prime substituents is gas or fluorine, and n is an integer selected from 0, 1, 2, and 3. A better case is: each of Chi 2 and C is hydrogen, C1-C4-alkyl, unsubstituted, mono-, di- or tri-substituted phenyl, _〇R6 group (where ~ is Crc4 (Yodo group) or -CH (R7) W group (wherein W is -COOR7, where R " 7 疋 wind or 匚 1-〇4- 丨 group) substituent group is C "C4 surface group, C 丨 -C4 alkoxy or fluorine'η is an integer selected from 0, 1, and 2. This paper size applies to the Chinese national standard (CNS > A4 size (2IOX 297 mm)) (Please read the note on the back first Please fill in this page again) Set the policy of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 41136 ^ .... A7-^ _? Z___ V. Description of the invention (5) A better case is that r2 and each R3 are hydrogen , CrC ^ -alkyl, unsubstituted, mono-'di- or tri-substituted phenyl, · 0R6 group (where R6 is c rC) alkyl or -CH (R7) W group (where w Is -coor7, where R7 is nitrogen or C1-C2-rule), and the phenyl substituent is Ci-Cj》, Ci-C ^ pitoxy or fluorine 1, and η is selected from 0, 1, and An integer of 2. In the best case, R2 and each R3 are hydrogen'phenyl, fluorenyl, methyl, or fluorine. In Formula I, B and May be selected from the group consisting of (i) unsubstituted, mono-, di-, and tri-substituted arylphenyl and theophyl groups; (ii) unsubstituted, mono-substituted-substituted heterocyclic aryl groups * Pyridinyl, succinyl, benzodecan-2-yl, benzosan-3-yl, p-synyl, benzof-syn-2-yl, benzoylan-3 -yl, Dibenzofluorenyl, dibenzoanyl and carbazolyl, aryl and heterocyclic substituents are selected from the group consisting of hydroxyl, amine, crc6-alkylamino, dialkylamino, morpholino, Piperidinyl, 1-4 indolyl, pyrrolidinyl, i_imidazolinyl, 2-midol-1 -yl, 2-τ »pyridyl, p-pyridyl, 1_oxazine Base 'crc6 slope base, Ci-CJ pit group, CrC # oxy group, mono (crC6) alkoxy (C rC4) alkyl, propionyloxy, isobutenefluorenyloxy and oxin, among which halogen or (halogen ) The group can be fluorine or gas; (iii) The following formula HA and the group represented: (Please read the precautions on the back before filling out this page) 袈 ·-Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

Among them, ϋ can be carbon or oxygen, E can be oxygen or substituted nitrogen, when £ is -8-This paper size is applicable to China National Standard (CNS) Λ4 specification (210X297 mm > employee consumption of the Central Standards Bureau of the Ministry of Economic Affairs) Printed by the cooperative 41.136, V. Description of the invention (6) The 'DM substituent is selected from hydrogen C2-C6 ^^-s. ^ CrC6 ^. CrC ^; The element can be gas or fluorine: C6 linear group, CrC ^ oxy (c "C4m group 'C3_C6 cycloalkyl group, di (CA) alkyl group (C3-C6) cycloalkyl'-(Ci_c6) alkyl gauge group And halo (CrC6) cyclopoyl, the halogen group can be gas or chlorine 2 (v) the group represented by the following formula IIC 圏. \ Η .0 = 0 ^, ν II c where U may be hydrogen Or cr (: 4 alkyl, v may be selected from unsubstituted, mono- and di-substituted of phenyl, phenyl'furanyl, and fluorenyl, wherein the substituent of each of the radicals is Cl_C4 Alkyl, Ci_C4 alkoxy, fluorine or gas; or (V1) B and B 'together form an unsubstituted, mono- and di-substituted fluorene-9_ group or form a group selected from the group consisting of: C3 -C12 spiro-monocyclic hydrocarbon ring (such as: cyclopropylene, cyclobutylene, ring Base, cyclohexylene, cycloheptyl, cyclooctyl, cyclononylidene, cyclodecylidene, cycloidene (j-crackyl, cyclododecylidene), saturated C7-C12 Spirobicyclic hydrocarbon rings (eg, bicyclo [2.2.1] heptylene (ie, probornylidene)), 1,7,7-trimethylbicyclo [2.2.1] heptylene (ie, Borne alkenylene), bicyclo [3,2.1] octylene, bicyclo [3.3.1] nonidene-9-yl, bicyclo [4.3.2] undecyl), and saturated <: 7- (: 12 Spirotricyclic Hydrocarbons-9 · This paper size applies to Chinese National Standard (CNS) A4 specifications (2! 0 X 297 mm); ----- :! ^ ------ Order ------ 4-.I Γ Please read the cautions on the back before filling in this page. J Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 411361 A7 _________B7 V. Description of the invention (7) Ring (eg: Tricyclic [2.2.1.02'6] undecylidene alkyl, tricyclic [53112,6] subcarbon dicarbon, and tricyclic [3.3.1.13, 7] decylene (ie, gold Steel alkyl) 'wherein the fluorene-9-yl substituent may be selected from the group consisting of c alkyl, c ^ alkoxy, fluorine and gas. Preferably, B and B. are selected from the group consisting of not Substituted, mono-, di-, and tri-substituted arylphenyl groups; (ii) unsubstituted, mono- and di-substituted heterocyclic aromatic groups _Yl, benzopyridinyl_ 3 -yl, pcylenyl, benzo11 cylenyl-2, yl, benzoρyzenyl _ 3 _yl, dibenzylidene, dibenzofuranyl and Carbazolyl, phenyl, and heterocyclic substituents are selected from the group consisting of morpholino, piperidinyl, CrC4 alkyl, (^-(: 4 alkoxy, and halogen, where Milk; (iii) a group represented by formula IIA, where D is carbon and E is oxygen; each ^ is 匸-^ alkyl, CrC4 alkoxy, hydroxyl or halogen, and halogen is gas or fluorine; 119 and 111 ° is hydrogen or alkyl, respectively; m is an integer of 0, 1 or 2; (iv) cr rC4 alkyl, c alkoxy (C 丨 -C4) alkyl, and C3-C6 cycloalkyl: and (v) A group represented by the formula lie, wherein U is hydrogen or methyl, V is phenyl or a mono-substituted benzyl, and the phenyl substituent is a C1-C4 sulfo group, an alkoxy group, or fluorine; or (vi) B and B1 together form an unsubstituted or monosubstituted fluorenyl-9-yl group, <: 3-(: 8 spiro-monocyclic hydrocarbon ring, saturated C7-C10 spirobicyclic ring Smoke ring and saturated C7-C1 () spirotricyclic hydrocarbon ring. More preferably, B and Chuan are selected from the group consisting of (i) unsubstituted, mono- and di-substituted phenyl; (ii) unsubstituted, mono- and di-substituted heterocyclic arylpyridyl, respectively. Benzofuran-2-yl, benzofluoren-2-yl, dibenzopyrimyl and dibenzofuranyl, the phenyl and heterocyclic substituents are selected from the group consisting of morpholino, 11 Entertainment • Base and C〗 -C2 Entertainment * Milk Base; (丨 ii) Groups represented by Formula I1A-10- This paper size applies to China National Standard (CNS) A4 specification (210 × 297 mm) ^^ '1T% I-»--(Please read the notes on the back before filling out this page) Printed by the I Industry and Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs« 11362 A7 ..._ B7 V. Description of Invention (.) 8, where D Is carbon, and E is oxygen; each is 8 Crh alkyl, ^-(^ alkoxy or fluorine; R9 and Rio are hydrogen or Cl-C2 alkyl, respectively; m is an integer 0, 1 or 2; ( iv) or (vi) B and B 'together form an amidino-9-yl group, a norbornylene group, an orbornyl alkenylene group, a bicyclo [3.3.1] nonidene-9-yl group, or an adenyl steel alkyl group. The best case is: B and B 'are phenyl, methoxy-substituted benzyl, morpholine Substituted phenyl, dibenzofuran-2-yl or 2,3. Dihydrobenzofuran-5 -yl. More preferably, B and B1 are each selected from the group consisting of (i) unsubstituted, monobasic _, Di- and tri-substituted arylphenyl; (ii) unsubstituted, mono- and di-substituted heterocyclic arylpyridyl, furyl, benzo-2-anyl, benzofuran- 3 -yl, fluorenyl, benzopyrene-2 -yl, benzopyrimidin -3 -yl, dibenzopyrene, dibenzofuryl and carbazolyl, phenyl and heterocyclic substituents Selected from the group consisting of morpholino, piperidinyl, C rC4 alkyl, C alkoxy, and halogen, wherein the halogen or (halo) group is fluorine or gas; (iii) a group represented by formula IIA, where D is Carbon, E is oxygen; each ^ is 匸 alkyl, alkoxy, hydroxy or halogen, halogen is chlorine or fluorine; R9 * R10 is argon or Ci-C ^ alkyl; m is an integer of 0, 1 Or 2; (iv) C] -C4 alkyl, crC6 alkoxy (CrC *) alkyl and (33- (1; 6 cycloalkyl): and (v) a group represented by formula IIC, wherein, U is hydrogen or methyl, V is phenyl or mono-substituted phenyl, and the phenyl substituent is CrC4 alkyl, CVC4 alkoxy, or fluorine; (Vi) B and B1 together form unsubstituted or monosubstituted fluorenyl-9-yl or bornenylene, probornyl fluorenyl, bicyclo [3.3.1] nonon-9-yl or phenylene Gold steel alkyl. The best case is: B and B 'are phenyl, methoxy substituted phenyl, morpholino substituted phenyl, dibenzofuran-2-yl or 2, 3-Dihydrobenzofuran-5-yl-11-This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) I, -------- ^ ------ tr ------ PI-4 »-ί (Please read the notes on the back before filling this page) 411362 * A7 ___B7 V. Description of the Invention (9) 0 The compound represented by Formula I can be prepared from the following steps. The benzophenones represented by Formulas V and VA are commercially available or can be used by the Friedel-Crafts method using appropriately substituted or unsubstituted phenylhydrazone represented by Formula IV and commercially available by Formula III Prepared from substituted or unsubstituted benzene compounds. For this reaction, please refer to Friedel-Crafts and Related Reactions, George A. Olah, Interscience Publishers, 1964, Vol. 3, Chapter XXXI (Aromatic Ketone Synthesis), Ishihara, Yugi, etc. Human, " RegioselectiveFriedel-CraftsAcylationofl, 2,3,4-Tetrahydroquinoline and Related Nitrogen Heterocycles: Effect on NH Protective Groups and Ring Size (1,2,3,4-tetrahydro I »Quip strain and related nitrogen heterocycles Specific selection of Friedel-Crafts fermentation reaction: the effect of NH protecting group and ring size) ", J. Chem. Soc ·, Perkin Trans. 1, 3401-3406, 1992 = compounds represented by formula III and IV are dissolved in In a solvent (such as carbon disulfide or methane gas), react in the presence of a Lewis acid (such as aluminum chloride or tin tetragas) to form a corresponding substituted benzophenone represented by formula V (Or VA in reaction B). R and R · represent a phenyl substituent.

Response A Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economy-I---n I ..... I 1 ^ 1 1 ^ 1 ---:-^^ 1. I, (Please read the first (Note ^^ Please fill in this page) R COC1 〇

III IV R '-12- This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 411362 A7 _: _5Z__ V. Description of the invention (10) In reaction B, the formula VA is substituted or unsubstituted The ketone (where B and f may represent groups other than substituted or unsubstituted phenyl groups) is reacted with sodium acetylide in a suitable solvent (eg, anhydrous tetrahydrofuran (THF) to form formula VI Corresponding propargyl alcohol. The propargyl alcohol with a B or B1 other than a substituted or unsubstituted phenyl group can be made from a commercially available ketone, or from : A ketone prepared by reacting a base with a substituted or unsubstituted benzene, fluorene, or heteroaromatic compound. A propargyl alcohol with a B or B ′ group represented by Formula IIC may Manufactured from the method described in US Patent 5,274,132, column 2, lines 40-68.

Reaction B 0 II c / \ Β B1 f --1 m I n n I! — J n m I Ding-_ Ken (please read the precautions on the back before filling this page)

HO C = CH HC ^ CNa THF > Β ’, B *

VA VI Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The phenols represented by formulas VIII and XIII used in the preparation of pu: piran expressed by formula I can be prepared from those described in reactions C or D. In reaction C, 1,4-dihydroxy-2-arsanoic acid represented by formula VII and an alkyl gas (eg, methyl iodide) in the presence of ethyldiisopropylamine in an appropriate solvent (eg, anhydrous dihydrate) The reaction is metformamidine (DMF) to form the corresponding methyl-1,4-dihydroxy-2-theanate represented by formula VIII. This reaction is further described in the journal of Organic

Chemistry, 仏 (17), 3477 (1981). -13- The paper size applies to the national standard (CNS) A4 specification (2iOX297mm y 4113 like A7 B7

5. Description of the invention (q T

OH

COOtt + methyl iodide reaction c

OH

VIII In Reaction D, the 'substituted or unsubstituted acetophenone, dibenzone, or benzophenone (represented by formula IX) and dimethyl succinate (formula X) are in a base (such as: sodium hydride or Potassium tributoxide) is reacted in a suitable solvent (such as toluene or butyl HF) in the presence of monovalent Sa (represented by formula XI) to form a suitably substituted succinic arylene group. Compound XI is heated with acetic acid and anhydrous sodium acetate to form a corresponding acetate derivative represented by formula XII. The formula XII reacts with a hydrogen acid and an anhydrous alcohol (for example, anhydrous methanol) to form a corresponding resorcinol represented by the formula 乂 111. Reaction D is further described in John Wiley & Sons, Inc. of New York, published in the Physics Book orgganic Reactions, VI, Chapter 1, i_73. 1 .:-^^ 1 I-— HI I ^ 1 *-(Please read the precautions on the back and fill in this purchase)

S1T Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 14- This paper size applies to Chinese national standards (CNS > A4 specifications (210X297 mm >)

4113C A7 B7 V. Description of the invention (12 〇

Reaction D

(CH3CO) 2〇 CH3C〇〇Na

XIII

(Please read the notes on the back before filling this page) In the reaction E printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs, the propargyl alcohol represented by formula VI and the resorcinol represented by VIIIA (replaced further by (R3) n vm) couple to form 6-hydroxypyrene, represented by formula XIV. The 6-hydroxy substituent of the compound represented by the formula XIV can be converted into, for example, 6-hydroxyoxy by reacting with alkyl compounds (such as methyl iodide, ethyl iodide, fluorenyl bromide, etc.). To form a compound represented by formula XV. The compound represented by formula XV can be reduced to a 5-hydroxymethyl substituted compound represented by formula XVI by a method such as reducing it with lithium hydride (LAH) in an inert solvent such as THF. The 5-hydroxymethyl substituent in the compound represented by formula XVI can be derivatized in various ways. By using compounds of formula XVI and alkyl compounds (such as: methyl iodide, n-butyl bromide, benzyl bromide ... 15- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm)

0H

+ VIXXA 4113 "A7 B7 V. Description of the invention (13) etc.) In the presence of a base (such as potassium carbonate), the substituent is converted to an alkoxyfluorenyl group to form a compound represented by formula XVII. The compound represented by formula XVIII can be obtained by halogenating a hydroxymethyl group with a fluorenyl halide (e.g., acetyl chloride, benzamidine gas, etc.). In the third example, this hydroxymethyl group can be obtained by The reaction of trimethylsilyl in the presence of an acid acceptor (such as triethylamine) forms a trimethylsilyl ether represented by formula XIX.

Reaction E (Please read the notes on the back before filling this page)

THF

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

-16-

This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 411362 ΚΙ_Β7 V. Description of the invention (14) In reaction F, the propargyl alcohol represented by formula VI is coupled with the stub phenol represented by formula in A tea sulfan compound having a 6-aryl group, a 6-poyl group, or a 6 · hydrogen is represented by the formula XX. The compound represented by the formula XX can be reduced to a 5-trimethyl group represented by the formula XXI by using a method such as reducing it through an aluminium (lah) in a solvent such as THF. The 5-hydroxymethyl substituent of the compound represented by formula XXI can be derivatized in various ways. A compound represented by the formula XXII can be prepared by converting a substituent to a chloromethyl group by reacting a compound of the formula XXI with a sulfur gas. The 5-aminomethyl group of the compound represented by the formula XXΠ can be further derivatized by reactions known in the art, such as: by the reaction with primary, secondary or heterocyclic amines (such as propylamine, diethylamine, morphine) ... etc.) to give a 5-aminomethyl compound represented by the formula XXIII. Alternatively, the hydroxymethyl group in the compound of the formula XXI can be reacted with an alkyl dentate (e.g., fluorenyl iodide, propyl iodide, benzyl bromide, etc.) to obtain a compound represented by the formula XXIV. m- ^^ 1 I —ϋ — ^^ 1 I 11 ^ 1---I— HI τ », τ, a {Please read the notes on the back before filling in this 苋) Employees’ consumption of the China Railway Bureau The paper size printed by the cooperative is applicable to the Chinese National Standard (CNS) A4 (2Ϊ〇 × 297 mm) 411362 A7 B7 V. Description of the invention (15

Reaction F (R3) η

XXII

ΙΛΗ

_-1 ^ 1 m ^^ 1 t * 良 ^^ 1 1 ^ 1 ^^ 1--1 ~ ψ «3 ， νβ -II (Please read the precautions on the back before filling out this page) Ministry of Economy Central Standards The employees of the Bureau ’s consumer cooperative, Yinju 5-compound with amido group at the position, was prepared by a series of reactions in reaction G. Using potassium hydroxide dissolved in a mixture of water and alcohol, the resorcinol represented by the formula XIII is hydrolyzed to the carboxyresol by the formula XXV. By reacting with acetamyl gas, the acetamyloxy substituted compound represented by the formula XXVI can be obtained. This paper standard applies to Chinese national standard (CNS M4 specification (210X 297 mm) 411362 A7 B7. V. Invention Explanation (16) formula, the free hydroxyl group of the compound of the formula XX V is protected. The carboxy substituent of the compound of the formula XXVI is converted to acyl chloride by reacting with the sulfur gas to form the compound of the formula XXVII. , Secondary or heterocyclic amines (such as: propylamine, diethylamine, morpholine, piperidine, etc.) to obtain a compound represented by the formula XXVIII, the acid tritium gas of the compound of the formula XXVII is converted into amidino. By reacting with methanol in the presence of HC1 to obtain the fluorenol of XXIX, the fluorenyl substituent of a compound of the formula XXVIII is deprotected. The pyran bearing a 5-fluorenyl group represented by the formula XXX is prepared from the formula XXIX Between catechol and block propyl alcohol of formula VI.--1 1 ^^ (. ^^^ 1 I-1 ^ 1 I ------ • I '(Please read the (Please note this page, please fill in this page) Use Chinese National Standard (CNS) A4 (210 '乂 297 mm) 411362 A7 B7 V. Description of Invention (17

Reaction G

XXIX —I..-— —- ^^ 1 * IJR ^^ 1 m--^^ 1 ^ ij., Vs f, (Please read the notes on the back before filling this page)

XXV Engineering II

HO C = CH

The compound represented by Formula I printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs can be used in applications where organic photochromic substances can be applied, such as: eyeglass lenses (such as vision correction lenses, hand-held goggles, sunshade-20. China National Standard (CNS) A4 specification (210 X 297 mm) 411362 — A7 _________B7__ V. Description of the invention (18) Plates, camera lenses, windows, car windshields, transparent accessories for aircraft and cars (such as: sunroof, side Lights and rear lights) 'Plastic films and plates, fabrics and coatings (such as coating composition, such as paint) and identification marks on security documents (such as banknotes, passports and driver's licenses have authorization or identification functions Document). The color of Trisylvanum represented by Formula I can be changed from colorless to yellow to red / purple. Examples of piperans that are intended to be included for the purposes of the present invention are as follows: (a) 2,2-bis (4-methoxy Phenyl) -5-hydroxymethyl-6-methyl-9-methoxy-2H-fluorene [l, 2-b] pyran; (b) 2,2-bis (4-methoxybenzene ) -5-hydroxymethyl-6-methyl-2H-naphthalene [1,2-b] pyran; ((〇2,2-bis (4-methyl (Oxyphenyl) -5-ethoxymethyl-6-phenyl-211-fluorene [1,2-b] pyran; (d) 2- (4-methoxyphenyl) -2- (2,3 -dihydrobenzyl-5-yl) -5 -branzyl-2-yl-9-methyl-9-methoxy-2H -fluorene [l, 2-b] p ratio; (e) 2,2-bis (4-methoxyphenyl) -5-hydroxymethyl-6-methoxy-2H-fluorene [1,2-b] p ratio; (f) 2,2 -Diphenyl-5-methoxyfluorenyl-6-methoxy-211-fluorene [1, 2-15] pyran; E1 4 «— ^ — 1- J (Please read the notes on the back before filling this page) (g) 2,2-spiro-adamantyl-5 -ethoxyfluorenyl-6-fluorenyl-2H-fluorene [1,2-b ] p thanan; (h) 2,2-bis (4-methoxyphenyl) -5-trimethylsilyloxymethyl-6_methoxy-2 fluorene-naphthalene [1,2-b ] Pyran; (i) 2- (4-methoxyphenyl) -2-tert-butyl-5-methoxymethyl-6-phenyl-9-methoxy-2H-fluorene [l , 2_b] pyran; and -21-This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) A7 B7 printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (19) (j ) 2- (4 -methoxybenzene ) -2- (2,3 -dihydrobenzofuran-5-yl) -5 -Arylidene-6-fluorenyl-9-methoxy · 2Η-Pho [l, 2-b] p ratio Mum. The present invention also intends to include the combination of organic photochromic piperidine represented by formula I with other suitable organic photochromic materials, so that plastic lenses containing these photochromic materials will form near neutral gray when exposed to ultraviolet light. Or brown tone. For example, a compound that converts to yellow can be used in combination with a compound that converts to a suitable purple to form a brown hue. Similarly, a compound that is orange when colored and a compound that is appropriately blue will form a gray tone when used in combination. The combination of the aforementioned photochromic materials can also be used in applications other than spectacle lenses. The novel piperidine compounds of the present invention (such as the foregoing) can be used alone or with complementary photochromic compounds (such as: at least one organic light sensor with an activated absorption maximum between about 400 and 700 nanometers) A color-changing compound or a substance containing the compound) may be used in combination, or it may be mixed (eg, dissolved or dispersed) into a polymeric organic main material used to prepare a light-sensitive color-changing object, so that the compound or a mixture of compounds exhibits a proper hue when activated. The first type of supplementary organic photochromic substances used in the organic photochromic naphthyl piperanes of the present invention are those whose active absorption maximum position appears in the visible light range greater than 570 nm (eg, between approximately 570 to 700 mmol). Micron range). These materials are essentially blue, blue-green, or blue-violet when exposed to ultraviolet light in a suitable solvent or matrix. Many such compounds are described in the published literature. For example, 'In addition to other compounds, Spiro (^ 卜朵琳) Qin Mingying has been described in US Patent Nos. 3,562,172, 3,578,602, 4,215,010, and 4,342,668; there is a Spiro (indole, lin) benzopyridine of these substituents has been described in U. s. Patent -22- This paper size applies to Chinese national standards (CNS> A4 specifications {210X297 mm) (Please read the back Please fill in this page for the matters needing attention.) Order the Central Sample Rate Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, India Fan A7 B7 V. Description of Invention (20)

No. 5,405,958; Spiro (pyridoline) pyridinobenzoxazine has been described in US Patent No. 4,637,698; Spiro (benzene)? Pyridoxan and Spiro (benzene n | f indole) The hydrazine has been described in U.S. Patent No. 4,931,219; the snail (benzo 4 voice and 11 breaks) has been described in Japanese Publication 62/195383; the snail (yin | ** guolin) benzopyridine has been Described in U.S 'Patent No. 4,816,584; snail (4 Buduo Lin) benzoρ biran, snail ("? 丨" Duolin) Fanwei ran and snail (4 丨 lin) 4 La and u ratio Mum has been described in, for example, US Patent No. 4,880,667; the benzo p ratio of the 2-position having a nitrogen-containing substituent on the chewing ring has been described in U, S. Patent No. 4,818,096. Phi Bran is also described in John Wiley & Sons, Inc. of New York, published in 1971 and edited by Glenn H. Brown, Techniques in Chemistry, III, " Photochromism ", Chapter 3. Organic Photochromic Discoloration of the Invention The second type of supplementary organic photochromic substances used by pipiran is those in the visible light range where the maximum absorption activation occurs in the range of about 400 to less than 500 nanometers. These substances Substantially yellow-orange when exposed to ultraviolet light in a suitable solvent or matrix. Such compounds include certain chromenes, i.e., benzopyrans and pyripranes. Many such chromenes are described in published In the literature. For example, US Patent 3,567,605, 4,826,977, and 5,066,818. Other examples of benzo? Pyran and naphthane that can be used in combination with the reacted pyrene include: at the alpha position of the oxygen atom of the ppyran ring Those with a spiro gold steel alkyl group, these compounds are described in US Patent 4,826,977; 2H- ^ with certain substituents on the 5th and 6th carbon atoms of the tea portion of naphthalene;-[l, 2-b] pyridine Compounds such as those described in US Patent Application Serial No. 08 / 164,1 87, filed on Dec. 9, 1993; have at least one para position at the 3-position of the pyran ring. This paper size is suitable for Chinese storehouse samples (CNS > A4 size (210X297mm)) ----------------- Packing--U (Please read the note on the back first Please fill in this page again) -Order 411362-A7 _B7 V. Description of the invention (21) 3 phenyl substituent 3 Η-荇-[2,1-b] p In US Patent 5,066,818; there are some substituents on the 8th carbon atom and some substituents on the 7th or 9th carbon atom, and these substituents are all located in the naphthalene portion of the naphthyl piperane. 1-b] pyran compounds, such compounds are described in U.S. Patent Application Serial No. 08 / 080,246, which was filed on June 21, 1993; the 3 position of the pyran ring is substituted with (i) an aryl group And (ii) 3H · 荇 [2,1-b] pyrans substituted with a 5- or 6-membered ring and a benzene substituent fused to its 3 and 4 carbon atoms are described in US Patent 5,384,077; Or an unsubstituted 5 or 6-membered heterocyclic ring with the g, i or 1 side of the dipiperin-3H-tea [2, I-b]! 1 to 3 compounds were described in 1994 4 U.S., Patent Application Serial No. 08 / 225,022, which was filed together on the 8th; the 8th carbon atom of the fluorene portion of pueraran was replaced by, for example, a methoxy group, and the I ° base compound is described In US Patent 5,238,931; sulfan compounds (such as 3-aryl-3-arylalkenyl piperans) are described in US Patent 5,274,132; and the fifth carbon atom is, for example, ethoxyl, Superseded by [2, l-b] Pyran is described in U.S. Patent 5,244,602. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) The third type of supplementary organic photochromic substances used in the organic photochromic chromatophores of the present invention is the largest active absorption A position occurs between about 400 to about 500 nanometers and another absorption position occurs in the visible range between about 500 to about 700 nanometers. These materials are essentially yellow to violet and yellow / brown to violet / gray when exposed to ultraviolet light in a suitable solvent or matrix. Such compounds include certain substituted 2H-phenanthro [4,3-b] pyrans; substituted 3H-phenanthro [4,3-b] pyrans; and benzopyran compounds such as: A substituted or unsubstituted heterocyclic ring at the 2-position of the nan ring (such as: benzene-24-This paper is applicable to the Chinese national standard (CNS) Λ4 specification (2Ϊ0 x297 mm) A7 __B7 V. Description of the invention (22) And, the selenium or benzoanan ring) is condensed with the benzene part which is lumpy. The latter is described on August 8, 1994-U.S. Patent Application No. 08 / 286,039 and U.S. Patent 5,411,679, which filed applications. The photochromic article of the present invention may optionally contain one or more photochromic compounds as required. A single type of photochromic compound or a mixture of multiple photochromic compounds can be used to achieve certain activated colors (such as: medium gray or brown). The compound of the present invention (also a second type of photochromic compound) can be used here The first supplementary organic photochromic substance (ie, the color is changed to blue, blue-green, or blue-violet) is used in combination, or with other organic photochromic compounds described in the aforementioned second type of photochromic compounds And use. The first or second group of photochromic compounds or mixtures of these compounds can be used in combination with the third group (i.e. those whose color changes from yellow to purple and yellow / brown to purple / gray) as described herein. The amount (or ratio) of the photochromic substance described herein may be such that the main material (application of photochromic compounds or mixtures of compounds or addition of such compounds) has the desired final color (eg, as much as possible) A neutral color close to the color provided by an activated photochromic compound). Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs .............. --II I---I. ^^ 1!: 1 I--— ^^ 1 ^ 11— (Please read the Note again on this page) The gray in the gray color corresponds to a fairly average absorption in the visible range between 400 and 700 nm. Medium brown has a greater absorption in the 400-550 nm range than in the 550-700 nm range. Another way to describe color is to describe with color coordinates. This description describes the amount of color other than the light-emitting factor, that is, its color development. In the CIE system, the color coordinates are derived from the ratio between the three primary colors 値 and its sum (eg, χ = χ / (Χ + Υ + AZ) and y = Y / (X + Y + Z). The CIE system can be described The color is drawn on the color chart, usually based on the color -25- table paper rule i applies the Zhongguanjia standard (匚 ^^ specifications (training secret-411362) printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 5 The invention description (23) is a graph of coordinates X and y. Please refer to Principles of Color Technology by FW Bullmeyer Jr., and Max Saltzman, 2nd edition, published by John Wiley & Sons, Inc., New York, 1981. As used herein, " XM and " y " in the color coordinates of the near-neutral color that changed 40% of the color by being exposed to the sun's rays (Air Mass 1 or 2) are within the following ranges, respectively. : X = 0_260 to 0.400, y = 0,280 to 0.400. There is no special requirement for the amount of the photochromic substance or the composition containing the same applied to the main material. As long as the amount is sufficient to activate the photochromic discoloration by activation It can be recognized by the naked eye. Generally, this amount is called the light-sensitive discoloration amount. The particular amount used usually depends on the color intensity after the desired light irradiation and the method of adding or applying the photochromic substance. Basically, the more the mass of the photochromic substance applied or added, the more the color intensity will be increased to A certain limit 値. The relative amount of the aforementioned photochromic compounds used can vary, partly depending on the relative intensity of the color of the active species of such compounds. Generally, based on the surface area of the organic main material to which the photochromic substance is added or applied, light The color-changing substance is present in an amount of about 0.05 to 1.0 (eg, about 0.1 to about 0.45) mg / cm2. When using a mixture of the aforementioned organic photochromic supplements, the ratio between these materials, that is, (1st class / 2nd class), (2nd class / 3rd class), and (the chant of the present invention / other second class compounds) from about 1: 3 to about 3: 1, such as: From about 075: 1 to about 2: 1. The weight ratio of the first, second and third types of organic photochromic supplements can be from about 1: 3: 1 to about 3: 1: 3. Photochromic substances can be prepared by various methods described in this technique-28- This paper size applies to Chinese national standards (CNS) Λ4 specification (2) OX 297 mm (Please read the notes on the back before filling this page) • Binding 411362 A7 ____ B7 V. Description of the invention (24) Application or blending Into the host material (such as: polymeric organic host material). Such methods include dissolving or dispersing the photochromic substance in the host material, such as: incorporating the photochromic substance into the monomeric host between polymerization reactions The photochromic substance is absorbed by the polymeric organic main material in the material; the main material absorbs the photochromic substance by immersing the main material in a hot solution of the photochromic substance or by thermal transfer; The color-changing substance is interposed between adjacent main material layers in the form of an isolation layer (for example, it becomes a part of a polymer film and the photochromic substance is applied as a part of a coating layer on the surface of the main material. The so-called absorption effect " or " absorption " refers to the role of the photochromic substance penetrating into the main material alone, the photochromic substance entering the porous polymer with the help of a solvent, vapor phase transfer and other similar transfers mechanism. In applications such as medical or fashionable, compatible (chemical and color) shades (ie, dyes) can be applied to the main material to make it more aesthetically pleasing. The particular dyeing department used can be changed and depends on the requirements and results to be achieved. In one embodiment, a dye may be selected to supplement the color obtained by the activated photochromic substance, #: to achieve a more natural color or to absorb a specific incident wavelength. In another embodiment, the dyes can be selected to print n-si.---Mni — * ^^ 1 ^ 1--II-n IT * * '0¾. * V5 (Please read the notes on the back before filling in this page) When the photochromic substance is in an unactivated state, the main substrate has the desired hue. It is also possible to add an auxiliary material to the main material before, during or after the photochromic substance is added to the main material. For example, an ultraviolet light absorber may be added before the photochromic substance is applied to the main material, or the absorbent may overlap in the form of a layer located between the photochromic substance and the incident light (27-paper scale applicable Chinese National Standards (CNS) ---------- A7 B7 V. Description of Invention (25) (eg: superimposed on it). In addition, a stabilizer may be blended before the photochromic substance is applied to the main material to improve the photoembrittlement resistance of the photochromic substance. Stabilizers can be included, such as hindering amine stabilizers and monooxygen removers (eg, nickel ions that are mismatched with organic complexes). They can be used alone or in combination. Such stabilizers are described in U.S. Patent 4,720,356. Finally, a suitable protective coating can be applied to the surface of the host material. They may be resist coatings and / or oxygen-shielding coatings. Such coatings are known in the art. The host material is usually transparent, but can be translucent or even cloudy. The electromagnetic wave of the main material (this electromagnetic wave is used to activate the photochromic substance, that is, the ultraviolet (UV) wave constitutes the open form of the substance) and visible light (including the substance at the absorption wavelength of its activated form (eg, open form)) Part of it-it must be transparent. Preferably, the main color should not obscure the color of the activated form of the photochromic substance, i.e., the observer can easily perceive the change in color. More preferably, the main material object is a solid transparent or optically clear material, such as: materials suitable for optical applications, such as: flat and optical mirrors, windows, automotive transparent objects (such as windshields), aircraft transmission Light objects, plastic plates, polymer films, etc. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs I_— · ----- ^-赛-(Please read the precautions on the back before filling out this page) Can be used with the photochromic substances described here or Examples of the polymerizable organic host material used in combination include: a polymer (such as a polyol (allyl carbonate) monomer, a dimethacrylate diethylene glycol ester monomer, a diisopropenylbenzene monomer, and alkoxylation Homopolymers and copolymers of polyhydric alcohol acrylate monomers (such as ethoxylated trimethylolpropane tripropionate monomers); polyfunctional (such as: mono-, di-, tri-, Homopolymers and copolymers of tetra- or poly-functional) acrylate and / or methacrylate monomers, polyacrylates, polymethacrylates, poly (iso • 28-) This paper applies Chinese national standards (CNS) A4 size (210X 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 411U2 ,, A7 ------ B7__ V. Description of the invention (26) Butenoic acid CrC〗 2 Longyl ester) ( Such as: poly (methyl isobutyrate), polyoxy (alkyl butyrate) ), Poly (alkoxylated phenol methacrylate) (such as: polyethoxylated bisphenol A dimethacrylate) 'cellulose acetate, cellulose triacetate, cellulose acetate-propionate, cellulose Acetate-butyrate, poly (vinyl acetate), poly (vinyl alcohol), poly (ethylene gas), poly (ethylene gas), polyurethane, thermoplastic polycarbonate, polyester, poly (Ethyl terephthalate), Polystyrene, Poly (Methylstyrene), Copolymer (styrene-methyl methacrylate), Copolymer (styrene-acrylic acid 3), Polyethylene butylene Polymers of Yuehe Diphenylene Pentaerythritol Vinegar (ie, 'homopolymers and copolymers'), especially polymers of diethylene glycol vinegar with polyol (allyl carbonate) monomers (eg, bis (ene Propyl carbonate)) and propionate monomers. Blends of transparent copolymers and transparent polymers are also suitable as the main material. Preferably, the main material is an optically clear thermoplastic polycarbonate Polymerized organic resins (such as carbonate-linked resins derived from bisphenols and phosgene) Material 'This material is sold on the market under the registered name of LEXAN; a polyester, such as: materials sold on the market under the registered name of MYLAR: poly (methacrylate), such as those sold on the market under the registered name of PLEXIGLAS; Polymer particles of catechol (allyl carbonate) monomers (especially bis (fluorenyl carbonate) diethylene glycol vinegar), such as monomers sold on the market under the registered name of CR-3 9; and polyols (Allyl carbonate) (such as (Allyl carbonate) diethylene glycol ester) Copolymer polymer particles of copolymer and other copolymerizable monomer materials (such as vinyl acetate), such as: 80_90% two Copolymer of ethylene glycol bis (fluorenyl carbonate) and 10-20% ethyl acetate, especially 80-85% bis (fluorenyl carbonate) and -29- (please read the back first (Notes on this page, please fill out this page)

-, 1T This paper size applies Chinese National Standard (CNS) A4 specification (nox2? 7mm) 411362 Μ _Β7 ___ V. Description of the invention (27) Copolymer of 15-20% ethyl acetate, and with Copolymers of dipropionate-functional polyurethanes, such as those described in US Patent 4,360,653 and 4,994,208; and copolymers with aliphatic ureas whose terminal part contains dilute propyl or propionate functional groups , Described in U.S. Patent 5,200,483; Poly (vinyl acetate) 'Polyvinyl butyral, polyurethane, polymer of the following monomers: diethylene glycol dimethacrylate monomer, diisopropene Benzene monomer and ethoxylated trimethylolpropane triacrylate monomer; cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate-butyrate, polystyrene Copolymer of styrene with ethyl methacrylate, vinyl acetate and acrylonitrile. More specifically, the light-sensitive discoloration of the present invention and the optically clear organic resin monomers used in the manufacture of light-transmitting polymer particles (ie, materials suitable for optical applications, such as flat or corrective lenses, windows, and automobiles Transparent accessories). The refractive index of the optically clear polymer particles may be about 1.48 to about 1.75, such as about 1.495 to about 1.66. The following examples further illustrate the present invention. As those skilled in the art understand how to make various modifications and changes, these examples are for illustration purposes only. Example 1 Step 1 Printed by the Consumers ’Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ^ 1. II I ..... ·---IIIIVI: II II I ί— I: 丁 4, '* * -β (Please Read the notes on the back before filling this page.) Dimethoxybenzophenone (0.27 moles) was dissolved in a reaction flask containing 200 ml of saturated acetylene anhydrous tetrahydrofuran and stirred at room temperature. An 18% by weight suspension of sodium ethenylbenzene in xylene / mineral oil (0.3 moles of sodium acetylene) was added to the reaction flask, and the mixture was stirred. In a nitrogen atmosphere, stir at room temperature for 16 hours. 'Add 5% by weight to the mixture in the reaction bottle. -30- This paper size applies to China National Standard (CNS) A4 specification (2 〖〇X297mm） ) ~ ----- 411362 A7 __________B7 V. Description of the invention (28) A mixture of hydrochloric acid and ice. The resulting mixture was extracted with diethyl ether. The organic layer was separated, washed, filtered and dried over anhydrous sodium sulfate. The agent (diethyl ether and tetrahydrofuran) was removed under a vacuum, and an oily product containing bis (4-methoxyphenyl) -2-propyne · 1-ol was obtained, which was directly purified without purification. Used for the following steps. Step 2 1,1-Bis (4-methoxyphenyl) _2-propynyl-l-ol (approximately 0'025 mole) and 1,4-Ethyl-6-methoxy- 1-Methyl-2-methylacetate (5 g, 0.022 mol) was added to a reaction flask containing 200 ml of toluene and stirred. A catalytic amount of p-xylene-sulfonic acid (about 100 mg) was added, and the mixture was stirred for 4 hours. Then, the reaction mixture was poured into a 10% by weight sodium hydroxide solution. The organic layer was separated, washed with water, and dried by filtration through anhydrous sodium sulfate. Remove the remaining solvent (toluene) under argon. A silica gel column was used, and a 1: 3 mixture of a gas imitation and hexane was used as an eluent to purify the obtained oil. The photochromic fractions were combined, and the eluent was removed under vacuum. The resulting product was crystallized from hexane. The melting point of the recovered product was 132-133 ° C. Nuclear magnetic resonance (NMR) spectrum showed the structure of this product with 2,2-bis (4-methoxyphenyl) _5-methoxycarbonyl. 6-methyl-9-methoxy-2H-naphthalene [l, 2-b] pyran matches. Step 3 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ------- J --- „-I Wei --------- 1T (Please read the precautions on the back before filling this page) 2,2-bis (4-methoxyphenyl) -5_methoxycarbonyl-6-methyl-9-fluorenyl-2H-fluorene [l, 2-b] pyran (1.7 g, 0.0034 mo Ear) was dissolved in a reaction flask containing 200 ml of tetrahydrofuran and stirred. Carefully add bell aluminum hydride (0.13 g, 0.0034 moles), and stir the mixture at room temperature for 2 hours. Add 2-propanol, then Add 5% by weight hydrochloric acid solution. The resulting blend is -31-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 '乂 297 mm) 411362 A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Description of the invention (The 29 compound is extracted with two 100 ml portions of digas methane. The organic extracts are combined, filtered and dried over anhydrous sodium sulfate. The solvent (digas methane) is removed under vacuum. This product is crystallized from diethyl ether The crystals were collected by suction filtration. The shock point of the recovered product was 125-127 C. Nuclear magnetic resonance (NMR) spectrum showed the structure and 2,2-bis (4-methoxyphenyl) _5_hydroxyfluorenyl_6_methyl 9-fluorenyl-2H-fluorene [l, 2-b] P is more consistent than that in Example 2. Step 1 Potassium tributoxide (75 g, 0.75 mol) was added to a reaction flask containing 200 ml of toluene. The resulting paste was heated to a retorting temperature under a nitrogen atmosphere, while dibenzene was heated for up to 30 minutes A mixture of formazan (91 g, 0.05 mol), dimethyl succinate (90 g '0.62 mol), and toluene (100 g) was added thereto. After the addition, the resulting paste-like mixture was maintained at The reflux temperature reached 2 hours' and then cooled to room temperature. 400 ml of water was added and the mixture was stirred for 30 minutes. The aqueous layer was separated, acidified with dilute acid and extracted with 200 ml of toluene. The solvent was removed to give a viscous oil, which was subsequently cured 'containing 4,4-diphenyl-3-methoxycarbonyl-3-butenoic acid product. This material was used directly in the next step without purification. Step 2 The product from Step 1 was dissolved in a reaction flask containing 200 ml of toluene. To the reaction flask was added acetic acid (100 g) and anhydrous sodium acetate (15 g). The mixture was allowed to simmer for 17 hours. The resulting mixture was cooled to room temperature, and the solvent was removed under air. The reaction flask containing the obtained residue was added with digas methane (200 ml). Water was added to the reaction flask ( 200 ml), and then slowly add sodium carbonate solid 32- This paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 mm) ni ik mt J. •,-0¾ i (Please read the precautions on the back before filling (This page) DuPont A7 B7 printed by Shellfish Consumer Cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (30) until no more carbon dioxide is released. The two-gas radon pit layer was separated, washed with water, and the solvent was removed under a vacant space to obtain a viscous oil containing 丨 ethyl ethyl-3-methoxycarbonyl-4-phenylnaphthalene. Step IX 3 Methanol (400 ml) was added to the reaction flask containing 1-ethoxy-2-methoxyoxy-4-phenylnaphthalene obtained in step 2. Concentrated hydrochloric acid (2 liters) was added to the reaction flask and the mixture was heated to the return temperature. After 4 hours, the resulting mixture was cooled to room temperature, and the solvent was removed under a vacuum, and the crystals were collected by suction filtration. The collected crystals were washed with methanol and allowed to air dry. The melting point of the recovered product (100 g) was 174-176 ° C. Nuclear magnetic resonance (NMR) spectroscopy showed the structure of this product with 4-phenyl-3-methoxycarbonylfluorenol. Step 4 4-phenyl-3-methoxycarbonyl-fluorenol (2 g) obtained from Step 3 and 1,1-bis (4-methoxyphenyl) obtained from Step 1 of Example 1 _2_propyne- ^ alcohol (g) was added to a reaction flask containing 100 ml of toluene and stirred. The resulting mixture was heated to 40 ° C, and a catalytic amount (a few drops) of decadecylbenzoic acid was added (ie, an amount sufficient to give the mixture a deep red color). After 4 ×: stirring for 3 hours, the mixture was cooled and washed with water. The organic layer was separated and the solvent (xylene) was removed under reduced pressure. A silica gel column was used with a 2: 1 hexane: ethyl acetate mixture as the eluent to purify the resulting oil. The photochromic fractions were combined, and the solvent was removed under air. The obtained product (2.0 g) was crystallized from a hexane-diethyl ether mixture, and the crystals were collected by suction filtration. The melting point of the recovered product was 168-169 ° C. Nuclear magnetic resonance (NMR) spectroscopy showed the structure of this product and 2,2bis (4-methoxyphenyl) -5-fluorenyloxycarbonyl_6_phenyl-2H-fluorene-33-This paper is for Chinese country Standard (CNS) person 4 saying (210 X297 mm) (Please read the precautions on the back before filling this page)-installed ·

A7 _____________B7 V. Description of the invention (31) [1,2-b] p matches. Step 5 2,2 bis (4-methoxyphenyl) -5_methoxycarbonylphenyl-2H-tea [l, 2-b] pyran (100 g, 0.02 mo Ear) Dissolved in a reaction flask containing 300 ml of tetrahydrohanan and stir. To the stirred solution was carefully added Zhongming hydrogen (1.2 g '〇_〇32mol), and the mixture was heated to 4 (rc for 25 hours. After cooling to room temperature, 2-propanol was added, then 5% by weight hydrochloric acid solution. The resulting mixture was extracted with three 100 ml portions of diethyl ether. The combined organic extracts were filtered and dried over anhydrous sodium sulfate. The solvent (diethyl ether) was removed under vacuum. The resulting The residue was crystallized from diethyl ether, and the crystals were collected by suction filtration. 3 g of the desired product was recovered. Nuclear magnetic resonance (NMR) spectrum showed the structure of this product and 2,2 bis (4-methoxyphenyl)- 5-Hydroxymethyl-6-phenyl-2H-pyrene [l, 2-b] p matches the ran. Example 3 The 2,2-bis (4-methoxyphenyl) obtained from step 4 of Example 2 -5 -Methoxycarbonyl-6-phenyl-2H-fluorene [l, 2-b] pyran (2.0 g, 0.004 mole) was dissolved in 200 ml of digas methane and 1,2 equivalents of triethylamine In the reaction bottle. After the reaction mixture was heated to the retorting temperature for 4 hours, acetamidine gas (0.37 g, 0.0048 mol) was added thereto. After cooling to room temperature, diethylammonium was added and the Removal of by-products (triethylamine hydrogenated hydrogen). Purify the product using a silica gel column with chloroform as the eluent. Combine the photochromic fractions and remove the solvent under empty space. The recovered product (0.2 G) Crystallized from diethyl ether. Nuclear magnetic resonance (NMR) spectroscopy showed the structure of this product and 2,2-bis (4-methoxyphenyl) -5 -ethoxymethyl-6-phenyl-2H-stub [l, 2-b] Pyran matches. -34- The paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) ---, --- MJ—J--packing ------ (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs f. Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economics B7 * '-.... ---- V. Description of the Invention (32) Example 4 Step 1 Add 3-methoxycarbonyl-4-methyl-7-methoxy_1-fluorenol (12 g) to a solution containing potassium hydroxide (25 g) and water (250 g). Ml) and ethanol (50 ml) in a reaction flask. The mixture was heated in a steam bath for 6 hours, cooled to room temperature, and poured into an excess of cold dilute (about 5% by weight) hydrochloric acid. The resultant was removed by suction filtration The solid product was dried to give 11 g of the desired product, 3-carboxy-4-methyl-7-methoxy-1-fluorenol. Step 2 The 3-carboxy-4-methyl-7 obtained from step 1 -Methoxy-1-fluorenol (11 g) was added to a reaction flask containing 100 ml of digas methane. Triethylamine (10 g, 0.1 mole) was added with stirring. The resulting exothermic reaction mixture Cool in an ice bath. While maintaining the temperature at 5. (: at, add acetamidine gas (4 g, 0.05 mole) dropwise. The mixture was stirred at 5 ° C for 15 minutes, and then warmed to room temperature, at which time it was stirred for another 15 minutes, and then poured into an excess of cold dilute (about 5% by weight) hydrochloric acid. The precipitated product was removed from the two-phase mixture by suction filtration, washed with clean gas, and dried to obtain 11 g of the desired product. The NMR spectrum showed the structure of this product and ^ ethyloxy-3-carboxyl. _4-Methyl-7_methoxyfluorene matches. Step 3 Add 1 · ethoxyl-3_carboxyl_4_methyl_7_methoxyfluorene (11 g) from step 2 to a reaction flask containing 20 ml of sulfur trioxide. The mixture was heated in a steam bath. After about 30 minutes, when the HC1 was completely released, the excess sulfur gas was removed in a rotary evaporator to obtain the acid tritium chloride-35 in a solid form. n- i nn ^^^ 1 KJ—. tn ^^^ 1 nn-,-^ Λ% Affairs and words {Please read the notes on the back before filling out this page) 41136: A7 B7 Staff of the Central Government Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperatives. 5. Description of the invention (33). This 1-ethoxylated 3-oxycarbonyl-4-methyl-7-methoxy moss product was used directly in the next step without purification. Step 1 Add a half portion of the 1-ethoxy-3-hydroxycarbonyl-4-methyl-7-methoxyfluorene from step 3 to a mixture containing digas methane (50 ml) and piperidine (4.25 g, 0.05 mole) and triethylamine (5 g, 0.05 mole) in a reaction flask. After the addition was complete, excess cold dilute (about 5% by weight) hydrochloric acid was added and the resulting solution was mixed. The organic layer was separated, and then washed with water, a low-concentration sodium carbonate aqueous solution, and water. The solvent (digas methane) was removed in the air to obtain the desired product as an oil. NMR spectrum showed this product The structure is in accordance with 丨 _Ethyloxy_ 3-piperidinylcarbonyl-4-methyl-7-methoxyfluorene. Step 5 Add a mixture (200 mL) of methanol and concentrated hydrochloric acid (2 mL) to the containing 1-Ethyloxy-3-piperidinylcarbonyl-4-methyl-7 · methoxyfluorene obtained in the reaction flask of Step 4. The resulting mixture was back distilled in a steam bath for 2 hours. Then, this The mixture was cooled to room temperature and poured into dilute hydrochloric acid. The resulting precipitate was removed by suction filtration, washed with water, and dried to obtain 4.8 g of the desired product in the form of crystals. NMR spectrum showed the structure of the product and 3-piperidinyl Carbonyl-4-methyl-7-methoxy-1-fluorene is in agreement. Step 6 3-piperidylcarbonyl-4-methyl-7-methoxy-l-theanol (2.5 from Step 5) G) and 1- (2,3-dihydrobenzofuran-5-yl) -1- (4-methoxyphenyl) -2-propyn-1-ol (2.5 g) was added to the product containing 1 g. 〇mL toluene in a reaction flask and stir. Heat the resulting mixture to 50 ° C, add a few drops of dodecyl alkyl, -36- This paper size applies Chinese National Standard (CNS) A4 specification (2Ι〇χ297) (Centimeter) ^ ϋ- ml n--I · 1H In k-I (Please read the back first Please fill in this page again.) Order A7 ________B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention (34) benzenesulfonic acid (enough to make the mixture produce a deep red). After 2 hours, the reaction mixture Cool to room temperature and add water. The organic layer was washed with water and the solvent was removed on a rotary evaporator. A crushed gel column was used, and a 1: 1 mixture of ethyl acetate and ethyl acetate was used as the eluent for purification. The resulting oil. The photochromic fractions were combined, concentrated and crystallized from a small amount of a diethyl ether-hexane mixture. The desired product was collected by suction filtration and dried to obtain 2.6 g of crystals with a melting point of 201 -203 ° C. Nuclear magnetic resonance (NMR) spectrum showed the structure of this product and 2- (4-methoxyphenyl) -2- (2,3-dihydrobenzofuran-5-yl) -5 -piperidinecarbonyl 6- Methyl-9-methoxy-2H-fluorene [l, 2-b] pyran is consistent. Example 5 Part A The blend of the photochromic piperidine and the polymerized sample of the example was tested by the following method. A review of an estimated 15 X 1 0.3 μm solution was added to a solution containing 50 g of a monomer blend (4 parts of ethoxylated bisphenol A diisobutyrate (BPA 2EO DMA), 1 part of polymer (Ethylene glycol) 600 diisobutyric acid vinegar and 0.033% by weight of azo (2-methylpropionitrile) (AIBN) in a bottle. If necessary, the piperidine was dissolved in a single solution by stirring and gentle heating. Body blend. After obtaining a clear solution, pour it into a flat mold with an inner size of 2.2 mm x 6 inches (15.24 cm) x 6 inches (15_24 cm). Seal this transfer mold and place In a horizontal airflow, temperature-programmable furnace, set the temperature program to increase the temperature from 40 ° C to 95 ° C in 5 hours, and maintain it at 95 ° C for 3 hours, and then before the curing cycle ends Reduce the temperature to 60 ° C for at least 2 hours. After opening the mold, use a diamond cutter to cut the polymer sheet into 2 inch (5.1 mm) test pieces. -37- This paper size applies China National Standard (CNS) A4 specification (2! 〇 < 29 · / mm) I 丨 — j — -installation ------ order (please read the note on the back first) Please fill in this page for further information) Consumption Cooperation by Staff of Central Bureau of Standards, Ministry of Economic Affairs, Du Printing 411362 A7 B7 V. Description of Invention (35) The photochromic test block prepared in Part A and Part A of the photochromic perception rate on an optical table Test. Before the optical table test, expose the photochromic test block to 365nm UV light for about 15 minutes to activate the photochromic compound, and then put it in a furnace at 76 ° C for about 15 minutes to make The photochromic compound fades or purifies the photochromic compound. The test cube is then cooled to room temperature, exposed to fluorescent light for at least 2 hours, and then covered before the optical table test at 7 5 T (23.9 ° C) At least 2 hours. This table is equipped with a 150 watt pneumatic lamp, a remote-control shutter 'as a heat sink for arc lamps, a copper sulfate bath, Schott WG-320 nanometer filter (for removal Short-wave ray), neutral density filter, and sample slot into which the test sample is inserted. The parallel beam of the tungsten filament lamp passes through this block at an angle close to this block. The light from the tungsten lamp passes through this block. And detection Connected optical filter. This optical filter allows some wavelengths to pass through in a way that simulates the perception of the naked eye. The change in optical density (A 0D) is measured by inserting the test block in a faded state into the sample slot and adjusting the transmittance To 100%, the shutter of the gas lamp is opened to make the test block in a faded state reach the activated (ie, darkened) state with ultraviolet light, and the transmittance of the activated titanium is measured, and according to the formula △ 0D = log ( 100 /% Ta) (where% Ta is the light transmittance in the activated state, the logarithmic base is 10) to calculate the change in optical density. △ OD / Min represents the sensitivity of photochromic compounds to the perception of ultraviolet light. The measurement method is: first exposed to ultraviolet light for 5 seconds, and then expressed on the basis of minutes. The saturated optical density (OD) listed in Table 1 was obtained under the same conditions as Δ OD / Min, but exposed to UV for 20 minutes. Listed in Table 1 -38- 1 This paper size is applicable to Chinese National Standard (CNS) A4 size (210x297 cm) (Please read the precautions on the back before filling this page).

1T 411362 A7 B7 V. Description of the invention (36) λιη3χ is the absorption position of the activated (colored) form of the photochromic compound in the composition of diethylene glycol bis (allyl carbonate) in the visible light spectrum. The fading rate (T1 / 2) is required to remove half of the activated piperan in the test box at room temperature (75 ° F, 23.9 ° C) after the activation light source has been removed. time. The results of the compounds of the examples are shown in Table 1. Fish 1 Fading sample λ △ OD / Min △ 〇 D @ Compound max α See light 0.65 > 800 seconds c Please read the notes on the back before filling out this page) Printed by the husband and prospective bureau member of the Ministry of Economic Affairs, X Xiaowu Cooperation Seal ¾ The results listed in Table 1 show 2H- 荅 [1,2-b] py The rate of fading of the ran is excellent due to the 5-position substituent. By way of example, compounds 1 to 3 have an acceptable fade rate, while compound 4 has a much slower fade rate. All the four compounds in the examples had high OD saturation (i.e., activation strength) and high coloring rate (i.e., sensitivity). Although the present invention has been described with reference to specific details of specific embodiments, it is not intended to limit the present invention to some extent with these details, and the present invention is limited only by the scope of the appended patent applications. -39 times the scale is applicable to one Chinese standard (CNS) A4 specification (21〇 > < 297mm)

Claims (1)

No. 851139 Petition for Amendment of Chinese Patent Application Range (July 1989) Product Λ8 B8 Patent Application Scope Correction Year a 89. 7. 2〇 M 1. A piperidine compound with the following structural formula , Β 'Β' Please read the note on the back of the note by the Central Ministry of Economic Affairs of the Central Bureau of Commerce for the cooperation of shellfish, printed by Du, where (a) R 丨 is selected from the group consisting of -CH2x, _c (〇) y囷, where 'X-based hydroxyl, CrC4-alkoxy or c2-C4-fluorenyloxy, Y-OCH (Rn) Z group, or unsubstituted or mono-substituted is selected from the group consisting of 1 A heterocyclic group consisting of a phenyl group, a morpholino group, a hexahydropyridyl group, and a __pyrrolidinyl group, wherein Z is -C (0) R12 or -C00Rn, Ru and R12 are hydrogen or c rC4-alkyl and R 13 is hydrogen; the substituent of this heterocyclic ring is selected from the group consisting of C plant C4-alkyl and alkoxy: (b) R2 and each R3 are hydrogen, c 丨 -C4-alkyl, unsubstituted Or mono-substituted phenyl '-0R6 group', wherein each of the 6-series (^ _ (: 4 alkyl or mono-substituted phenyl (Crc3) alkyl 'phenyl substituents are alkyl, crc4 alkoxy, Gas or fluorine 'η is an integer selected from 0, 1, 2 and 3; and (c) B and B' may be selected from the group consisting of: (i) unsubstituted, mono- and di Substituted phenyl; (ii) unsubstituted, mono- and di-substituted heterocyclic aryl, pyridyl, sulfanyl, benzene Sulfur-2-yl, benzofuran-3-yl, p-secenyl, benzthiophene-2-yl, benzopyrimidin-3-yl, dibenzofluorenyl, dibenzo I r Fill in the 1 page of the noon page. Paper Standards (CNS) Α4 · (2Ι () × 297 Public Manager) Article 851139 The Chinese Application for the Amendment of the Patent Scope (July 89) Product Λ8 B8 The Amendment of the Patent Scope Year a 89. 7. 2M 1. A piperidine compound having the following structural formula , Β 'Β' Please read the note on the back of the note by the Central Ministry of Economic Affairs of the Central Bureau of Commerce for the cooperation of shellfish, printed by Du, where (a) R 丨 is selected from the group consisting of -CH2x, _c (〇) y囷, where 'X-based hydroxyl, CrC4-alkoxy or c2-C4-fluorenyloxy, Y-OCH (Rn) Z group, or unsubstituted or mono-substituted is selected from the group consisting of 1 A heterocyclic group consisting of a phenyl group, a morpholino group, a hexahydropyridyl group, and a __pyrrolidinyl group, wherein Z is -C (0) R12 or -C00Rn, Ru and R12 are hydrogen or c rC4-alkyl and R 13 is hydrogen; the substituent of this heterocyclic ring is selected from the group consisting of C plant C4-alkyl and alkoxy: (b) R2 and each R3 are hydrogen, c 丨 -C4-alkyl, unsubstituted Or mono-substituted phenyl '-0R6 group', wherein each of the 6-series (^ _ (: 4 alkyl or mono-substituted phenyl (Crc3) alkyl 'phenyl substituents are alkyl, crc4 alkoxy, Gas or fluorine 'η is an integer selected from 0, 1, 2 and 3; and (c) B and B' may be selected from the group consisting of: (i) unsubstituted, mono- and di Substituted phenyl; (ii) unsubstituted, mono- and di-substituted heterocyclic aryl, pyridyl, sulfanyl, benzene Sulfur-2-yl, benzofuran-3-yl, p-secenyl, benzthiophene-2-yl, benzopyrimidin-3-yl, dibenzofluorenyl, dibenzo I r Fill in the 1 page of the noon page paper size (CNS) Α4 · (2Ι () × 297 public director) 41136 ^ as B3 C8 —-—______ D8__ VI. Scope of patent application — furyl and carbazolyl, each The substituents of phenyl and heterocyclic ring are selected from the group consisting of morphino, hexahydropyridyl, Cl-C4 alkyl, Cl_C4 alkoxy, and nanin. The nanin or (ii) group is fluorine or (Iii) a group represented by the following structural formula: Among them, D is a carbon and E is oxygen; each 118 is a CrC4 alkyl group, a C1-(: 4 alkyl group, a light gas, or a form I R_9 and R_i〇 are a chlorine or C1-C4 alkyl group; m is 0 An integer of 1, 1 or 2; (iv) CrC4 alkyl, CrC4 alkoxy (CrC4) alkyl, and C3-C6 cycloalkyl; and (v) a group represented by the following structural formula: \ / H / C = C, u V Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ----------- ^ ------ Order f poems before reading the note ^^ on the back before filling this page) , U is hydrogen or methyl, V is phenyl or mono-substituted phenyl 'The substituent of the phenyl is alkyl, CrC4 alkoxy, fluorine or gas; or (vi) B and B' together Substituted or monosubstituted fluorene · 9 · group 'or selected from the group consisting of saturated C3-C8 spiro-monocyclic hydrocarbon ring, saturated 0? · C10 spirobicyclic hydrocarbon ring and saturated C7-C1 () spirotri A group of cyclic hydrocarbon rings. -2- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 2.3. According to the i-piperan of item i in the scope of the patent application, its tn is an integer selected from 0 and 2. According to 荇 piperan of item 2 of the scope of the patent application, wherein (3) 1 ^ #-(: Η2 × group or -C (〇) Y group is trapped ', wherein x is a hydroxyl group, C1-C4-alkoxy group or c2_c4-fluorenyloxy, γ is an unsubstituted or monosubstituted heterocyclic ring selected from the group consisting of 1-pyridinyl, morpholino and hexahydropyridyl; (b) R2 and each r3 are hydrogen , CrC2 · alkyl 'unsubstituted or mono-substituted phenyl, -OR6 group (alkyl group therein), the phenyl substituent is Cj-C2 fluorenyl, C ^ -C ^ alkyloxy or Fluorine; (c) B and B 1 may be selected from the group consisting of: (i) unsubstituted, mono- and di-substituted heterocyclic aryl, pyridyl, epi-2-anyl, benzene Benzethenyl-2-yl, dibenzotephenyl, and dibenzofuranyl 'The phenyl and heterocyclic substituents are selected from the group consisting of morpholino, hexahydropyridyl, C, C2 alkyl, and C丨 -C2 alkoxy group; and (ii) the group of the following structural formula: (Please read the note on the back before filling out this page) Order the Central Samples Bureau of the Ministry of Economic Affairs, Printed Consumers Cooperatives (Re) m where 'D is carbon and E is oxygen; each 118 is C rC2 alkyl, C1-(: 2 alkoxy or fluorine; 119 and 111 () are hydrogen or CrC2 alkyl, respectively; m is , An integer of 1, or 2; and (iii) B and B, which form an unsubstituted or mono-substituted sub-substrate-9- 3 This paper uses China National Standard (CNS) A4 specifications (2 丨 0 X 297 (Mm) ABCD 411362 6. The scope of patent application, borneolene, probornolene, bicyclo [3 3 1] nonidene_ 9 _ or adamantine. 4. According to the patent application Three piperidines, wherein R 1 is hydroxymethyl, ethoxymethyl, morpholinocarbonyl or hexahydropyridylcarbonyl: R2 and each R3 is hydrogen, phenyl'methoxy or methyl B and B, respectively, are phenyl, methoxy substituted phenyl, morpholino substituted phenyl, dibenzofuran-2 · yl or 2,3-dihydrobenzofuran_5 5. The piperazine compound according to item 丨 of the scope of patent application, which is selected from the group consisting of: (a) 2,2-bis (4-methoxyphenyl) _5 · hydroxymethyl _6_methyl_9_methylamino-2H · fluorene [l, 2-b] pyran; (b) 2,2-bis (4-methoxyphenyl) -5-hydroxymethyl-6-phenyl_2 only-items: [1,2-b] pyran; (c) 2,2-bis ( 4-methoxyphenyl) -5-ethoxymethyl-6-phenyl-2H-tea [l, 2-b] i »pyran; (d) 2- (4-methyllactylbenzene Group) _2- (2,3 · dihydrobenzopfran-5-yl) -5. Piperidinylcarbonyl-6-methyl-9-methoxy-2H-fluorene [1,2-b] Blowing; (e) 2,2-bis (4-methoxyphenyl) -5-hydroxymethyl-6-methoxy-2H. Moss [1,2-b] p ratio; (〇2 , 2-diphenyl-5-methoxymethyl-6-methoxy-211-fluorene [1,2-fluorene] pyran; (g) 2,2-spiroadamantyl-5 -acetamidine Oxymethyl-6-methoxy-2H-a [l, 2-b] pyran; This paper size is applicable to Chinese bacteria standard (CNS) A4 specification (2 丨 0X297 mm) (Please read the back first Please fill in this ear for the matters needing attention) Binding-booking S 8 8 8 ABCD Printed by the Shell Standard Consumer Cooperative of the Ministry of Economic Affairs Central Standards Bureau of the Ministry of Economic Affairs Printed by the Consumer Standard Cooperative of the Central Standards Bureau of the Ministry of Economy -Bis (4-methoxyphenyl) -5-trimethylsilyloxymethyl-6-methoxy-2H-fluorene [l, 2-b] 〇biran; (i) 2- ( 4-A Phenyl) -2 -Third-butyl-5 · methoxymethyl-6 • phenyl-9-methoxy-2H-fluorene [l, 2-b] pyran; and (j) 2- (4-Methoxyphenyl) -2- (2,3-dihydrobenzofuran-5-yl) -5-aminomethyl-6-methyl-9-methoxy-2H-fluorene [1 , 2-b] pyran. 6. According to pipiran of item 1 of the scope of patent application, wherein: (a) R ^ -C (0) Y group 'wherein γ-_CH (Ru) z group is solid, where R11 is hydrogen and z is -COOR2, where r12 is crc4-alkyl; (b) R2 is hydrogen; (c) R3SCt-C4-alkyl 'η is 1; and (d) B and B1 are phenyl, respectively. 7. According to Wanhao Nan, No. 6 of the scope of patent application, it is 匚 i_c2-pit base. 8. According to Article 7 of the scope of patent application, r3 is methyl. 9 · —A light-sensitive color-changing article, which includes a polymer-type organic main material and a light-sensitive color-changing compound according to any one of claims 1 to 8 of the patent application scope, wherein the polymer-type organic main material is selected from the group consisting of : Polyacrylate, polymethacrylate (CpCu alkyl methacrylate), polyoxy (alkylene methacrylate), poly (alkoxylated methacrylate), weavin acetate, cellulose Triacetate, cellulose acetate-propionate, cellulose acetate-butyrate, poly (vinyl acetate), poly (ethyl cockyl alcohol), poly (ethylene gas), poly (ethylene chloride), Thermoplastic polycarbonate, polyurethane, polyurethane, poly (vinyl terephthalate), polystyrene, poly (α_ -5- This paper size is applicable to China National Standard (CNS) A4 Washer (210 X 29? Mm) --Γ ---- ^ #), .---------- Order (Please read the notes on the back before filling in this page j ._ D8 ._ D8 Central Ministry of Economic Affairs Lead the Bureau of Zhenggong Consumer Cooperatives to print «. VI. Patent Application (methylstyrene), copolymerization (phenethyl ethyl methacrylate), Polymers of poly (styrene-acrylonitrile-acrylonitrile), polyvinyl butyraldehyde, and the following monomers: polyenzyme (allyl carbonate) monomers' polyfunctional acrylic monomers, polyfunctional isobutylene Acid ester monomer, dimethacrylate diethylene glycol ester monomer, diisopropenylbenzene monomer, alkoxylated polyhydric alcohol acrylate monofluorene, and difluorene propylene pentaerythritol ester monomer. 10. The light-sensitive color-changing article according to item 9 of the scope of patent application, wherein the polymerizable organic main material is a solid transparent homopolymer or copolymer, and is selected from the group consisting of poly (isobutyrate) and poly (bisisobutene). Glycol esters), poly (ethoxylated bi-yearly 'A-isobutyric acid vinegar), thermoplastic polyacetate, poly (vinyl acetate), polyvinyl butyral, polyurethane and Polymers of the following monomers: bis (allyl carbonate) diethylene glycol ester monomer, dimethacrylate diethylene glycol monomer, diisopropylfluorenylbenzene monomer, and ethoxylated trimethylolpropane tripropylene Phosphonate monomer. 11. The light-sensitive color-changing article according to item 9 of the patent application scope, wherein the light-sensitive color-changing substance is present in an amount of 0.05 to 1.0 mg / cm2 based on the surface area of the organic main material to which the light-sensitive color-changing substance is added or applied. 12. The light-sensitive color-changing article according to item 9 of the patent application scope, wherein the article is a lens. 13. The photochromic article according to item 9 of the scope of patent application, which comprises at least one additional organic photochromic compound having an activation absorption maximum between 400 and 700 nm. 14. The light-sensitive color-changing article according to item 9 of the applied patent, wherein the other organic light-sensitive color-changing compound is selected from: -6- This paper size applies to China National Standards (CNS) A4 specification (2 丨 0X 29 ? Mm) ί—f —I fl —ii-.. ,, »^ 1 I ^ I (Please read the precautions on the back before filling out this page) Order the Consumer Cooperative of the Central Economic and Trade Bureau of the Ministry of Economic Affairs to print« 11362 SI C8 ----------- D8_ VI. Patent Application Range (a) Organic photochromic substances with at least one absorption peak in the visible range in the range of 400 and below 500 nm; ( b) An organic photochromic substance having an absorption range between 400 and 500 nm in the visible range and an absorption peak between 500 and 700 nm in the visible range (C) at least one active absorbance greater than M in the visible range. Nanometer organic photochromic substances; and (d) a mixture of the organic photochromic substances. 15. The photochromic object according to item 14 of the scope of patent application, wherein the additional organic photochromic compound is an organic photochromic substance having a maximum activated absorption peak greater than 570 nm in the visible light range. 16. The photochromic article according to item 17 of the scope of patent application, wherein the additional organic photochromic compound is selected from the group consisting of spiro (indololine) pyridoxine, spiro (indololine) pyridinebenzoxazine , Spiro (benzene 4-doline) oxaxazine, spiro (benzene p5) yin yin ran, spiro (indo y lin) benzopyrene, snail (4 yoke lin) benzopyran, spiro (啕 声 啦) 荇 喃 喃, spiro (啕 味）) p quinopyran, spiro (β indolin) pyran, 3 Η-荇 [2,1-b] pyran, 2 菲 phenanthrene [4,3-b] leaf dipper, 3 Η-phenanthro [1,2-b] p ratio; benzo p ratio compound and a mixture of these photochromic substances. This paper size applies to China® Standards < CNS) A4 (210X297 mm) (please read the note on the back before filling this page) I I n I n. N n 4 I-I 1 ^ 1 1— — »H I