JPS60112880A - Photochromic compound and product containing same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

The present invention relates to photochromic compounds and compositions and articles containing such potochromic compounds. Photochromism is a color change that occurs when exposed to radiation containing ultraviolet a, such as sunlight or the light of a mercury lamp.
This is a reversible phenomenon in which the compound returns to its original color if the radiation is then stopped or the compound is stored in the dark. Compounds exhibiting this phenomenon are called "N-potochromic compounds." Prior Art Various types of photochromic compounds have been synthesized and proposed for use in applications that cause discoloration or darkening when exposed to sunlight. Patent No. 3.36.2./
No. 7.2, No. 3.57g, No. 602, No. G, , 215
．． No. 010, No. 1, 3, 2. / The spillo (Indrin) naftoxazine compound as described in L and 3 is a special profit for Zanglass and eye lenses. Such photochromic compounds, whether in crystalline form or as a solution or dispersion in a transparent medium, rapidly change color from colorless to six colors when exposed to sunlight or ultraviolet light and cannot be left in the dark. Depending on, or (
・It returns to its original colorless state in the absence of strong ultraviolet rays. According to the present invention, a novel photochromic compound represented by the following general formula (2) is provided. In the general formula I above, R is selected from the group consisting of C alkyl, phenyl, phen(C,) alkyl, arynol, and mono- and di-substituted phenyl groups,
The phenyl substituent is selected from C□-C4 alkyl, C-C alkoxy. Preferably, 1 B is a C1-04 alkyl group or a phenyl or benzyl group. R2 of formula I, [(3 is each C□-C5 alkyl, phenyl, and mono- and di-substituted phenyl,
benzyl, selected from group 6, or combined with b
- forms a cyclic ring selected from the group consisting of an alicyclic ring containing g carbon atoms (including spiro carbon atoms), norbornyl, adamantyl; Phenyl It IJ! ,! It can be selected from C-04 alkyl and C-04 alkoxy groups. Preferably, R2 and R3 are each C□ -C
Selected from 5 alkyls. When one of R2 or R3 is a tertiary argyl group such as tert-butyl or tert-amyl, the other is preferably an alkyl group other than a tertiary alkyl group. R%R, each is hydrogen, Cney05
Alkyl, halogen, C, -C, alkoxy, nitro,
selected from the group consisting of cyano, CCB alkoxycarbonyl. R,,R. may be present at any available carbon atom of the indolino moiety of the compound, i.e., the 5th or 6th or 7th position, preferably, the substituent R
4. When R1) is other than hydrogen, these substituents are present in the indolino moiety C) at the ri and 5 or 5 and 6 or da and 7 or 6 and 7 carbon atoms. do. Although any chlorine, ie, chlorine, bromine, iodine, fluorine, can be used, chlorine, bromine, and especially chlorine are preferred. Preferably R,, R5 is hydrogen, C1-C
, alkyl, chlorine, bromine, and C1-05 alkoxy. Of particular interest are those in which R is C1-C4 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, nibutyl, ibutyl, tert-butyl, and R2 and R3 are each methyl. or ethyl or phenyl, and is a photochromic compound represented by the general formula I in which each of R4 and RI5 is hydrogen, methyl, methoxy or chloro. The photochromic compound of the present invention includes benzene, toluene, chloroform, ethyl acetate, methyl ethyl ketone, acetone, ethyl alcohol, methyl alcohol, acetonitrile, tetrahydrofuran, dioxane, methyl ether of ethylene glycol, dimethyl formamide,
It can be dissolved in common organic solvents such as dimethyl holpoquinde, methyl cellosolve, morpholine, ethylene glycol, and can also be dispersed in medium including water, alcohol, and other solvents. The sleeve of solvent used to dissolve the photochromic compounds of the invention, when applied to the host material,
The IJ must be of sufficient intensity to provide a potochromic composition that provides a photochromic amount of the compound gold in the composition. The photochromic compounds of the present invention are dissolved in a colorless or clear solution prepared from a transparent polymer, a copolymer or blend of such transparent polymers, and a suitable organic solvent, such as seven or more organic solvents listed above. It can also be dissolved in the polymer of the transparent host material described below. Examples of such solutions include polyvinyl acetate/acetone solution, nitrocellulose/acetonitrile solution, polyvinyl chloride/methyl ethyl ketone solution, polymethyl methacrylate/acetone solution, acetyl cellulose/dimethylformamide m solution, polyvinylpyrrolidone/acetonitrile solution. Contains melting, polystyrene/benzene solution, ethyl cellulose/methylene chloride i671N 75j. The photochromic solution or composition is applied to a transparent support such as triacetyl cellulose or polyethylene terephthalate or Barytanagi, dried and colored to W color by UV light and colorless KfA by removal of the UV source. A photochromic material can be obtained. The photochromic compounds of the present invention, or compositions containing them, may be applied to or incorporated into solid transparent polymeric materials or synthetic plastic host materials. Preferably, the host material is an optically transparent material, such as a material suitable for ophthalmic devices such as wearing lenses or for applications such as windows, windshields, etc. The host material containing the photochromic compound of the present invention can be used for photochromic plastic films, sheets and lenses, such as lenses for sunglasses, ski lenses, etc.
% can be used in the manufacture of sun visors, Gamera lenses and filters. 1. Optical elements used in this specification. The term "toy" refers to a lens and a transparent body.
cies l. Examples of transparent host materials that can be used with the photochromic compounds of the present invention include polymers of polyol (allyl carbonate) monomers, polyacrylates, poly(alkyl acrylates) such as methyl polymethacrylate, )
, cellulose acetate, cellulose triacetate, cellulose acetate 70-lobionate, cellulose acetate butyrate, bo1
(vinyl acetate poly(vinyl alcohol), poly(vinyl alcohol), polyurethane, 3417 carbonate, polyethylene terephthalate, polystyrene, poly(styrene-methac 1-noryl acid methyl copolymer), poly(styrene-ac+70
Nitrile) copolymer, polyvinyl butyral. Clear copolymers and transparent 71ζ remer films. Lends are also suitable as host materials. Preferably, the host material is a polycarbonate LEXIGLAS trademark, such as polycarbonate dioxydiphenol-2,2-propylene, sold under the EXAN trademark. Polymethyl methacrylate; polyol (such as materials sold in
copolymers with vinyl acetate, such as diethylene glycol bis(allyl carbonate) gO- Copolymer with 9θ% vinegar ff vinyl lθ-.2θ
Copolymers with 2096 - optically transparent polymeric organic materials made from niacetyl cellulose, cellulose propionate, cellulose butyrate, polystyrene and its copolymers with methyl methacrylate, vinyl acetate, acrylonitrile, and cellulose acetate butyrate. be. Polyol (allyl carbonate) monomers that can be polymerized to form the host material include allyl carbonates of linear or branched aliphatic or aromatic liquid polyols, such as aliphatic glycol bis(allyl carbonate) compounds or It is an alkylidene bisphenol bis(allyl carbonate) compound. These polymers can be referred to as unsaturated polycarbonates of polyols, such as glycols. These seven snails are
Methods known in the art, such as U.S. Pat. No. 2,370.36
It can be produced by the method described in No. 7, No. 1, 4tθ3, 113. Polyol (allyl carbonate) has the above general formula l

[wherein, R is a group derived from an unsaturated alcohol, usually an allyl-substituted allyl group, R' is a group derived from a polyol, n is an integer of 2-5,
Preferably -. The allyl group R may be substituted in the -position by a nitrogen, especially chlorine or bromine, or an alkyl group containing l-da carbon atoms, generally a methyl or ethyl group. The R group can be represented by the general formula % (in the above general formula, Ro is hydrogen or) 1 which is a C-C4 alkyl group. Special examples of R include allyl, cochloroallyl, copromoallyl, -monofluoroallyl, -methylallyl, coethylallyl, coisopropylallyl, λ-n-propylallyl, -n-butylallyl. It will be done. Most commonly, R is an allyl group H2C=C
HCH2-. R' is a polyvalent group derived from a polyol, which can be an aliphatic or aromatic polyol containing 2 or 3 or 2 or 5 hydroxy groups. Typically, the polyol contains two hydroxyl groups, ie, a glycol or a bisphenol. Aliphatic polyols may be linear or branched and have 1θ carbon atoms. In general, aliphatic polyols are alkylene glycols having 11 carbon atoms or poly(C2-C,+ alkylene glycols,
Examples include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol,
Or diethylene glycol or triethylene glycol. The aromatic polyol can be represented by the general formula (2). (Yamanaka, Al) -21+lfi (/,) groups derived from acrylic aliphatic hydrocarbons, such as alkylene or alkylidene groups having 1 carbon atoms, such as methylene , ethylene, dimethylmethylene (isopropylidene), Ra represents a lower alkyl substituent of /-3 carbon atoms, and p is θ or 1 or 2 or 3. Preferably the hydroxy group is ortho or para IJ Special examples of R' groups include ethylene (-CH2-CH2-
), trimethylene, methylethylene, tetramethylene,
Ethylethylene, pentamethylene, hexamethylene, -
1. such as monomethylhexamethylene, octamethylene, decamethylene. l-Alkylene group containing 70 carbon atoms: -c+Q-o CH2-1-CH2-CH20C
H2CH2, CH20CH2CH2-1CH2CHsi
Alkylene ether group such as CH20CH2CH2Cl-12-: -C)-12CI(2-0-CH2C
)-(, -0-CH2CH2-, -CH2CH2CH2
-0-CH2CH2CH3-0-C)IQCH2CH2
Alkylene glycol groups such as -: -CH2CH2
-0-Go-○-CH2CH2-1-CH2CH2-0
-CH2CH2-0-Co-0-CH2CH2-0-C
alkylene carbonate and alkylenoether carbonate groups such as H2CH2-; and impropylidene bis(p-phenyl)-j-1, i.e. /ij, n) >l!4, R ' is -C
1-i2cl-IQ- or -CI-12CH2-Oc
l-+, c112- or 1082CH2-0-CI-
12C)+2-O-CI-12CI-12-. 'l'k of polyol (allyl carbonate) monomer
Other examples include diethylene glycol bis(, 2-chloride, ethylene glycol bis(allyl carbonate), diethylene glycol bis(, 2-methallyl carbonate), diethylene glycol bis(, 2-methallyl carbonate), (allyl carbonate), triethylene glycol bis(allyl carbonate) propylene glycol bis(,2-ethyl allyl carbonate) 1./,
3 ~ Propanediol bis(allyl carbonatene, /
I3-butanediol bis(allyl carbonate), /
, l/-1-butanediol bis(,2-bromoallyl carbonate), dib ['' pyrene glycol bis(allyl carbonatene, trimethyl L/:/glycol bis(2-ethyl allyl carbonate, pentamethylene glycol bis() 1 CH2 =Cl-1-CH2-0-C-0-CH2-CH
2-0-CH2CH2-1 O-CH2CH2-0-C-0-CI-12CH=C- 0-CH2CH2-0
-C)-12CH2O-1 C-0-CH2-CH=CH2Vl Diethylene glyco-rubis(allyl carbonate group CH=CH-〇)-1-0-C-0-(,;H2CH2
-0-C-0-CH2-2$1 CH=CH,VIF Ethylene glycol bis(allyl carbonate). Diethylene glycol bis(allyl carbonate) is preferred. Method of producing polyol (allyl carbonate) monomer, i.e. polyol (or allyl alcohol)
For the method of preparation by phosgenation of and subsequent esterification with allyl alcohol (or polyol), the monomer product may include related monomer species in which the moiety that binds the allyl carbonate group contains one or more carbonate group alloys. There is sex. These related monomer species are represented by the general formula (■). In the above general formula (1), R is as defined above, Rb is a covalent group derived from a diol, such as alkylene or phenylene, and S is an integer of λ-1. The related monomer species of diethylene glycol bis(allyl carbonate) can be represented by the general formula IX. 1 CH2=CH-CH2-0-(J-0-CH2CH2-
0-CH2-OH2-01 -C)5-o-CH=-CHFCH2■ In the above general formula (1), 5 is an integer of 5. The polyol (allyl carbonate) monomer typically has a 2-, IOM weight factor of 0.
Related monomer species can be referred to as mixtures, i.e., 2.3.11. It can be present as a mixture of substances denoted by S equal to yx. Additionally, partially polymerized forms of polyol (allyl carbonate) monomers can also be used. In that embodiment, the monomer is thickened by 0 heat) or a small amount, such as θ5-75 parts/10θ parts monomer (p
Partial nailing using a hm l sieve to give a more viscous and thicker material with less gel content @ polyol (allyl carbonate) as used herein
Monomer or similar names, such as diethylene glycol bis(allyl carbonate), shall mean and include the monomer or prepolymer of that name and the related monomer species contained therein. The amount of photochromic compound or composition containing the compound applied to or incorporated into the host material is not critical and will generally achieve the desired color intensity and photochromic properties of the composition upon irradiation. Depends on the method used to mix or apply. Typically, the more photochromic compounds added, the greater the color intensity. Generally, such quantities can be described as photochromic quantities. Typically, the amount of photochromic compound incorporated into the host material ranges from about .theta..theta./-about .lamda..theta.I, more usually from about 0.05 to about 70% by weight, based on the weight of the host material. Stated another way, the proliferation of photochromic compounds used to produce photochromic effects typically occurs on the surface of the host material regardless of the thickness of the host material article. The photochromic compound ranges from about 1 to about 1/θ x photochromic compound per n''). Thus, the photochromic compound is present in high concentrations in thin samples, film dimensions or coatings, and in low concentrations in thick samples. Ethanol solutions of the photochromic compounds of the present invention are typically colorless or pale yellow or green or orange in color.These solutions rapidly turn purple or yellow when exposed to ultraviolet light; Removal of the source returns the original color or colorless state. Such color changes occur many times (E
-UT ability. The photochromic compounds or compositions of the present invention can be applied to or incorporated into post materials by methods known in the art. Methods of sintering include dissolution or dispersion of the photochromic compound into the host material, i.e. absorption of the photochromic compound into the host material by immersion or thermal transfer or coating (Imblbatlon
J, and the incorporation of a photochromic compound as a separate layer between adjacent host material layers. N absorption (
imblbat 1on)”or 1absorb(im
The term ``bibe l'' refers to the diffusion of a photochromic compound alone into a host material, solvent-assisted diffusion, confiscation of a photochromic compound into a porous polymer, vapor phase transfer, and other such transfers. For example, the hapotochromic compound or composition of the present invention is mixed with a superimposed composition which, when cured, forms a chemically transparent polymeric post material; And this polymerizable composition can be cast as a sheet or lens, or can be formed into a sheet or lens by injection molding or other methods. or by dissolving or dispersing in alcohol or other solvents or solvent mixtures and then immersing the host material in a bath of such solution or dispersion for several minutes to several hours, e.g. 3 minutes to 2-3 hours. The bath can be absorbed into the solid post material.The bath is usually at an elevated temperature, usually 1.50-1
It is in the range of 20°C. The host material is then removed from the bath and dried. (cll photochromic compounds and compositions can be applied to the surface of the post material by conventional methods such as spraying, brushing, spin-coating or dip-coating from a solution or dispersion of the photochromic compound in the presence of a polymeric binder. The photochromic compound can then be absorbed into the post material by heating the host material, for example in a dryer, at a temperature in the range of 0-1 g for 1 minute to several hours. fdl 10 g F2 absorption r ] In one variant, the photochromic compound or composition is placed on a temporary support, e.g.
It can be applied onto a sheet of kraft paper, aluminum foil, polymer film or cloth, then placed in contact with the post material and heated, for example in a dryer. tel photochromic compound? It can be dissolved or dispersed in a transparent polymeric material and applied to the surface of the host in the form of an adherent film by any suitable method such as spraying, brushing, spinning or dipping. Additionally, the photochromic compound can be incorporated or applied to the transparent polymeric material by any of the methods described above, and then the photochromic compound can be incorporated into the transparent polymeric material by any of the methods described above and then added to the photochromic compound as a separate layer in between the host material layer. You can enter the A category, White. The photocompound of the present invention has the corresponding 21.U
Nohydroquine ~ 'norrin compounds can all be synthesized by reacting with the corresponding indoline (with a base) or an indolium salt (e.g. with an iodine compound. This λ precursor material can be synthesized by reaction with a base such as triethylamine. In a suitable solvent, such as toluene or inpropanol, the reaction is refluxed until the reaction is complete. If the recovery is complete, and if it is a must-giri, then 4,110... products will be produced from the information-C. The present invention will now be further described by way of examples, but these examples are for illustrative purposes only, as many changes and modifications will be apparent to those skilled in the art. Examples/(Method A) A suspended S solution of 70 yd of S~nitrono-6-quinolinol (/74,9, θθ1 mol) in toluene was heated to /θ0-10f° C. without stirring. This heating @ suspension , triethylamine (002 mol j and 05 ml
Contains ethanol and gold. 3 or 4 t suspended in toluene of ? , 9 iodide/l, 3. s,6-bentamethyl-3-ethylindolium (001 mol) was added gradually over 1411/1). The flask containing the indolium iodide was washed with 3o-toluene and the toluene wash was added to the reactor. After refluxing the mixture in the reactor for an evening,
The reaction mixture was decanted and evaporated to near dryness. A mixture of a dark green gum and a small amount of crystalline material was obtained. The almost dry mixture was swabbed with 7-g fresh toluene, filtered, and washed once with 4'ml toluene. The p solution and washing solution were combined and evaporated. The crystalline material gradually became a gum over a period of S days. This thick gum k, 2-J ml! The sample was wiped with ethanol, subjected to FJ, washed with ethanol, and air-dried. A yellow-green powder (0, g/g) was swallowed. The P solution and washings were combined and evaporated to give an additional 0.2 g of green crystalline material, which was combined with the first crystalline product. The combined crude product was dissolved in acetone:(1-hexanol). A green microcrystalline powder θ714 was obtained, which was analyzed by nuclear magnetic resonance (NIv'l R1 spectroscopy and elemental analysis). , 3. O-tetramethyl-3-ethylspiro-indoline-λ, 3'[,?H]pyrido[,?
, , 2-f'][/, 4']benzoxazine]
1, from the same reaction components but produced separately f
``Also, the results of elemental analysis of the product showed that carbon 7'
Z 'l, 5 claws F (%, hydrogen bgg @ useless %, '?! element///1i1 (A-N in indulgence. These values are the theoretical value of carbon'/ 7.60 The concentration of hydrogen, 47 g M, and 7737 nitrogen are almost consistent with the equation. The solution was heated to reflux temperature.
71111y (0,007
2 moles) of iodination/, -y, 3. s,b-pentamethyl-3-ethylindolium f gradually added over 13 minutes) J! J I did. The resulting blue reaction mixture was refluxed for 2 hours and then allowed to cool to room temperature. This blue solution is
After evaporation overnight, crystals formed in the almost dry solution. The crystals were filtered, washed with about 200ml of Improper Tools, air-dried, and turned into a dark olive green powder (200ml).
Got 2&I. This powdered gold/20-gold was added to boiling n-hexane and all undissolved powder was removed by filtration. Activated carbon (isri'c) was added to the PM, stirred for several minutes, and then filtered. After removing the activated carbon, the volume of solution F was reduced to about 4 tons, and when it was left in the refrigerator overnight, yellow crystals were precipitated. After decantation, the yellow crystals were washed with fresh n-hexane and then air-dried. -ethylspiro[indoline-,2,3'[31-(]pyrido[3,2-f]
It was identified as [/, 1 benzoxazine]. Other photochromic compounds within the axis of general formula l can be combined with other indolines or indolium iodides containing S-nitroso-6-chiralinol and the substituents listed in Table 1, using toluene as the solvent. It was produced by reacting. When indolium iodide was used, triethylamine was also used as described in Example 1. The reaction products were purified by various conventional purification methods as exemplified in Example 1 and other examples illustrating the preparation of photochromic compounds of the invention. Table l, 2 CH3CH3CH3HH beige green powder 3C
H3CH3CH3S-CH3A-CH3 yellow green powder 4t
CH3CH3CH35-CH30H yellow powder, 5 CH
3CH3CH37-CH54-CIVA color powder 1-C
H3CH3C2H5, HH dark green paste 7 CH3C
H37,:Hill 1-IH dark green powder g C)-13 Phenylphenyl) l)-1 Yellow-green powder Unexampled/Ethanol solution of each compound of -7 when irradiated with ultraviolet rays at room temperature It changed to These solutions returned to their original hue or colorless after removal of UV light. Example 10 3θ-σ) A suspension of 5-nitrone-6-chiralinol (705110006 mol) in toluene was heated to reflux temperature with stirring. Add -〇- to this heated solution.
73') l/glycyl-3 dissolved in toluene
-Methyl-3-ethyl-methyleneindoline (00
06 mol) was added gradually over 20 minutes. After the mixture in the reactor was refluxed for 3 hours, the reaction mixture was transferred to a total evaporation dish and evaporated to almost dryness. This almost dry tM5 cell was swabbed with 7 ml of toluene, exposed to θ, and washed twice with 3 ml of toluene. Combine tPi liquid and VC liquid, evaporate,
The viscous dark color of the gum was gold. Redissolve the whole dried gum paste in 20 ml of diethyl ether, filter, and
The liquid was evaporated in the hood. When this ether solution/drop was diluted with ethanol and irradiated with ultraviolet light for about 3θ seconds at palm temperature, the solution changed color to 11 colors. This η color disappeared in about 5 minutes when the ultraviolet light was removed. The gum paste obtained by evaporating the ether solution was dried in a Kza desiccator for several days. This dry paste
Dissolved in /Ome toluene, dehydrated with left 6y aef thorium, filtered, and washed with 3- toluene. P
The AL, chlorine and gold were combined and evaporated in a hood to give a dark blue paste. Example 11 One part of the photochromic compound of Examples 1-/Q was mixed with 70 parts of a commercially available lacquer (3M Company "y7h-N[L2.
A solution of 233), 70 parts toluene and 19 parts methyl ethyl ketone was added to the lacquer solution. This lacquer solution was prepared from diethylene glycol bis(allyl carbonate) with a lambda of 54(7)(/1nJ).
X2. S 11 cm (/in l x thickness, 2.5 cm) was sprayed onto the surface of the polymer coupon. Dry the coated coupon at 760 °C for 10 min in an air dryer.
/J [It was heated. After cooling, connect the 1AWi lacquer with tape C and JP4, and wipe the surface gold with a cloth moistened with setone. Also 1~
Ta. The photochromic sensitivity of this potochromic tablet to the artificial Ll-pressure change (1 test was conducted. The results are shown in Table 3. Table 2/7/, 1.3 J S'), 2 /1. g O,'l/I'1,? 7.2 /13 II/ 11.6n θ'itg tts S -θ/A g 6 - θg9 1g 7 - θro/,! l za 37 θ, 29 2/ 7 g θg 0. 26 itノ 59 θ6F -NO / ΔT R - Artificial sunbC; Decrease in visible) C transmittance induced after irradiation minute fphotopic) Determine υ1 using one filter) So ΔOD- minute artificial day) and Sgθ- produced by irradiation
Change in saturation optical density constant at 1ll11 within 6,20 nm WVAJA.
Example 1 A prior art photochromic compound was treated in the same manner as described in Example 1. 1 from diethylene glycol bis(allyl carbonate)! ! ! I applied it to the coupon I left behind. The photochromic sensitivities of these articles are shown in Table 3 in comparison to the articles from Example-13. These photochromic compounds can be represented by the following general formula. In the above general formula, R4, R5, R6, and X are as shown in Table 3. 3rd Table 11 +1'iθ θ3/l, 29 θ, 2311g
θ Dal HC1-1,,0341C31 port θ7666
09gCl-13CH, 334θ3i 5? θ6s
'7,2 i/, 3 Example/3: A suspension of 5-nitrono-6-chirol/-l (0,32 & % θ()03 mokl in toluene of 1 The heated 1ltj t'A Q was dissolved in λθml of toluene containing triethylamine (0006 mol) of θ60y (i'75!<0.003 mol). Iodide l.-1-dimethyl-3,3-bis(p-methoxyphenyl)
Gradually add indium for about 20 minutes.
] Shita. The mixture in the reactor was maintained at approximately /θθ°C for 25 hours and the extent of reaction was monitored by total thin layer chromatography (TLC). The reaction was almost complete after 7 hours. After 15 hours at about 100°C, an additional 077 g (θooi mole J of 5-nitron-6-chiralinol was added to the reactor, but about 1
Even after 2 hours at 00°C, complete reaction of the indolium iodide reaction component was not obtained. The solids in the reaction mixture were separated by decantation and the remaining liquid was evaporated to near dryness. Olive green crystals were formed in this almost dry and hardened paste. This almost dry product was quenched with 7 ml of fresh toluene and
Filter and wash slowly with 3 ml of toluene. The multilayered crystalline powder product did not dissolve in toluene. This insoluble crystalline powder was washed with ethanol and air-dried to obtain an olive green powder (079 g). A sample of this powder was dissolved in ethanol and irradiated with ultraviolet light (3b 6 nm) for about 3θ seconds. The solution turned from light green to blue and returned to light green when the UV light was removed. EXAMPLE//lt J S A suspension of 5-nitroso-A-ky/linol (1,:19 g, 000 g mol) in mg toluene was heated to about 70[theta]C with stirring. This heated suspension contains 714 triethylamine (0016 moles), ? 29 @ clouded in S ml of toluene! ;g
Iodination of /, 2. j,4-tetramethyl-3,3--
Spiro(cyclohexyl)-[JH]indolium e:
Added gradually over zo-3o minutes. The progress of the reaction was checked by TLC. The mixture in the reactor is heated to about /θ0℃
After 3 hours at room temperature, the reaction mixture (dark brown solution) was evaporated to near dryness. T! +All 61 pastes
V for a few minutes with nl's fresh toluene? Insoluble matter was removed by filtration, and the resulting solid f3z was washed with 2 me of toluene. The P solution and the washing solution were combined and evaporated to obtain a dark brown paste (,2,,O'7jri'a=.
of ethanol and the resulting solution was exposed to ultraviolet light (36 Am) at room temperature. The solution turned light in color and returned to its original color in about 2 minutes after the UV source was removed. Example is Following the procedure of Example/J, 2.2 g (0,007 mol) of 5-nitrone-ro-quinolitool t,t. -/7θ in toluene! y<oθ07 Morph/-Rue 3.5. The mixture was reacted with trimethyl-3-ethyl-J-methyleneindoline at about 70[theta]C for about 3 hours. After evaporating the reaction mixture to almost dryness and quenching the resulting paste with Ame toluene for several minutes,
Filtered. The impurities were washed with lambda toluene. The P paste and washings were combined and evaporated to give a dark (greenish) brown paste (-99g). A small amount of this paste f J, −
The pale yellow solution dissolved in 3 ml of ethanol was exposed to ultraviolet light (36.4 nm).The solution turned green and returned to its original hue in about 2 minutes after removing the UV source. Example 1 According to the procedure in Example 1, a suspension of 4tg (691 mol) of 5-nitrone-6-chiralinol in toluene of θH was added to a solution of ug (θ02 mol). The iodination of 3, sag (1 mol of θθ) in toluene containing triethylamine was reacted with 3-diethyl-2,3,S,A-tetramethylindolium. After 3 hours of reaction,
A dark blue-green solution was obtained which was evaporated to almost dryness. The resulting paste was soaked for several minutes in 76ml of toluene and filtered. The solid obtained was washed with 2rn! of toluene and the washings were combined with Part P. The resulting dark solution was evaporated. 3.2 g of dark green paste was obtained.A small amount of this paste was subjected to photochromicity test using the method of Example 14t.
I took the exam. The ethanol solution of this paste was pale green, but it became a deep color when exposed to ultraviolet light. The solution returned to a light green color in approximately 3-'A minutes after removal of the UV light. Example 17 /7g I (001 mol) according to the procedure of Example /lI
5-nitrone-6-chiralinol; 2. ! ;7y/-butyl-7! -Ethyl-3,S,l,-trimethyl-nomethyleneindoline was refluxed in 70-g of toluene for 3 hours. The resulting product was a dark blue paste. A small ethanol solution of this paste was light to medium blue in color, but turned sky blue upon UV exposure. The solution returned to its original color after about 5 minutes when the UV light was removed. Example ig Following the procedure of Example/4t, 722 g of 5-nitrone-
6-Chiralinol k j Ome was suspended in hot toluene. This suspension was diluted with -〇- toluene/
70y of 1-glythyl-3,3,3°6-titramethyl-sumethyl/indoline was added slowly over about 70 minutes. The resulting mixture was refluxed for 3 hours. An ethanol solution of the resulting product turned dark blue upon exposure to UV light and returned to its original hue after approximately 5 minutes when the UV light was removed. The above operation was repeated using Improper Tool as a solvent. The product was a very dark green paste. Example/q 2o41. ! j<θθ07 molar Fisher base l
-benzyl-λ,5.6-)'trimethyl-3-ethyl-comethyleneylene/drine
/g procedure was followed. Ethanol j″rN produced by Xia et al. 11 is pale green at night, moderate N color VC change when exposed to the rays, and about 3-11 when UV rays are removed.
After a minute, it returned to its original hue. Example 2 θ boiling improvised in Knorr σ) θ 9.5' (0005
mole) of 5-nitronol, 6-quinol, 1nonol σ)
8fNVc, 1329 (0005 mol) dissolved in 25 ml of isobronoquinol, 3. S,l,-tetramethyl-3-phenyl-'-methyleneindoline was added slowly and the reaction mixture was refluxed for 1 hour.The resulting dark-colored reaction solution was evaporated overnight. A (almost black) colored gum was obtained. Further evaporation produced a hard cake which was considerably decomposed. This gum was subjected to -C chromatography on a thin layer chromatography plate and then placed in a silica gel matrix. The photochrominodei of the raw IU product was confirmed. A summary of the compound of Example 17-λ0 is shown in Table 49. 1g n-C4Hg CH3G1-13 CL (3CH
3 Dark green paste 19 Benzyl C2) (5G) (3
cl-13CH3 Dark Green Paste - θ CH3 Phenyl CH3 CHjl CH3 Dark tf Color Gum While the invention has been described in particular detail with respect to some of the embodiments thereof, such details do not fall within the scope of the claims. Nothing other than what is included or included should be construed as limiting the scope of the invention.

Claims (1)

[Scope of Claims] (C) The following general formula [in the above general formula, (al R-hcm-C8 alkyl, phenyl, phen(C-C,) alkyl, allyl, and mono- and di-substituted phenyl) and the substituent is C□
-04 alkyl and C□-05 alkoxy, (bl R2 and R3 are each C□-05 alkyl, phenyl, C-C alkyl, narahini l 4 C-057' alkoxy mono- and disubstituted phenyl,
selected from the group consisting of benzyl or combined with -
fcl R and R form a cyclic ring selected from the group consisting of an alicyclic ring containing g carbon atoms (including spiro carbon atoms), norbornyl, and adanthyl; C
6-furkyl, halogen, C1-C, alkoxy, nitro, cyano, C1-C8 alkoxycarbonyl]. L! l fal J is selected from the group consisting of C, -C, alkyl, phenyl, benzyl, each of tbl R2 and R3 is selected from C□-C5 alkyl, (cl each of R and R6 is hydrogen, C□- 02
A photochromic compound according to claim 3 selected from the group consisting of alkyl, chlorine, A, C, and C5 alkoxy. (3) R, R2, and R3 are methyl, and R and R5 is hydrogen, and R6 is a photochromic compound as described in claim 1.
is methoxy and R5 is hydrogen.Special If1: A photochromic compound according to Claim No. (/l) fl.
A photochromic compound according to claim 3, wherein 5 is chloro.
3-ethylspiro(indoline-2,3'[3H)pyridoC3,,2-f'Jc/, g]benzoxazine]
The compound listed in 'l'J' Claims No. (/)+e. "-(71 compound' proboscis/, 3.3.3.6-pentamethylspiro[indoline-,2,3'C3H]pyrido[
3,2-f] I, l, GJ benzoxazine] Claim g (g (/compound according to item 1. (8-) General formula [in the above general formula: selected from the group consisting of alkyl, phenyl, phen (C, C, l alkyl, allyl, and hepano and di-substituted phenyl, where the substituent is C
(bl R,8 and R8 are each selected from C, -C, alkyl, phenyl, C, -C4 alkyl, narahini C, alkoxy mono- and di-substituted phenyl) , benzyl, or a cyclic ring selected from the group consisting of -g carbon atoms (including a carbon atom), a cycloaliphatic ring selected from the group consisting of nor>1, runyl, atamantyl; (cl R4 and R5 are each selected from the group consisting of hydrogen, C, alkyl, ) ~ rogene, 1-C, 7) recoxy, nitro, cyano, and C□-C8 alkoxycarbonyl. A photochromic article comprising a solid transparent polymerized organic host material containing a photochromic compound represented by the following. f91 JM Li44 host month fi (but essentially,
Polymers of polyols (rlylcarbonate-1.), polyols (copoly7'- of 711lcarbonate-1 and vinyl acetate, poly-acrylates, poly(r-alkyl acrylates, acetylcellulose, triacetylcellulose,
Vinegar contains cellulose gropionate, cellulose acetate butyrate, poly(+:tg rt vinyl), poly(vinyl rlucolf, polycarbonate, polystyrene, poly(styrene-methacrylic late methyl) copolymer, poly(f-rene-acrylonitrile) Claims selected from the group consisting of copolymer, polyvinyl butyral!T fg
Photochromic article according to item 1. (10) The photochromic article according to claim 91, wherein the transparent host material is selected from poly[diethylene glycol bis(allyl carbonate)] and its copolymer with vinyl acetate. (//) The photochromic compound has the general formula [ In the above general formula, (at RItlC-04 is selected from the group consisting of alkyl, allyl phenyl, benzyl, (bl R, and R8 are each selected from C, alkyl, and icl R, and R5 are Each is hydrogen, C□-C
Q selected from the group consisting of alkyl, chlorine, bromine, and C□-05 alkoxy] The photochromic article according to claim (9). (12) General formula [In the above general formula, fat R is selected from the group consisting of c, -C4 alkyl, phenyl, and benzyl, (bl R2 and R3 are each selected from C, C, alkyl, cl R and R5 are each hydrogen, C□-C
2 alkyl, chlorine, odor 4Lc, 105 alumaxy; copolymer with vinyl acetate, polymethyl methacrylate, cellulose acetate, cellulose brochionate, cellulose butyrate, cellulose acetate butyrate, polystyrene, poly(styrene-methyl methacrylate minor copolymer, poly(styrene-acrylonitrile J copolymer) A photochromic article according to claim 722, wherein the photochromic compound is present in an amount of θO3-70% by weight. ) The host material is poly[diethylene glycol bis(
14. The photochromic article according to claim 13, wherein the photochromic article is selected from the group consisting of allyl carbonate) and its copolymer with vinyl acetate. (/S) The photochromic article according to claim 741, wherein R, J, R4, and R5 are methyl and R3 is selected from methyl and ethyl. (/6) The copolymer is diethylene glycol bis(allyl carbonate) ) gθ~90 arrogance and vinyl acetate lθ−λ
The photochromic f article according to claim 1, which is a copolymer with θ chi. (17) A host material selected from a homopolymer of polyol (allyl carbonate) and a copolymer of polyol (allyl carbonate) and vinyl acetate, and the general formula of the photochromic needle. yoCniec,,-t' selected from the group consisting of rukyl, phenyl, benzyl, (bl r(2, R3t, each one selected from C□-06, icl R4, R5+, each one hydrogen, C1-02
A photochromic element comprising a photochromic compound represented by the following from the group consisting of alkyl, chlorine, bromine, and C-05 alkoxy. (1gl polyol (rlyl carbonatene is diethylene glycol bis(allyl carbonatene), and the copolymer is a copolymer of diethylene glycol bis(allyl carbonate) gO-9θ and vinyl acetate io-, 20%, and photochromized 8' The sewing is θθ
5-7θ weight % of the optical element according to claim 1.17. (19) The photothalomic compound is R, R2, R4,
The optical element according to claim 17, wherein R6 is ethyl and R3 is a photochromic compound selected from methyl and ethyl. ■) If the element is a lens, the scope of claim vfJ (
The optical element described in /9). (,2/) The photochromic compound is fractionated over at least one surface of the lens.
The optical lens described in item 0).