JPS61159458A - Solid transparent polymer organic host material containing photochromic amount of photochromic compound - 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]

FIELD OF THE INVENTION The present invention relates to a solid transparent polymeric organic host material containing a photochromic amount of a novel photochromic compound. Photochromism is a color change that occurs when exposed to sunlight or light radiation containing ultraviolet radiation, such as the light of a mercury lamp, and then returns to its original color if the radiation is stopped or the compound is stored in the dark. This is a reversible phenomenon exhibited by compounds. Compounds that exhibit this phenomenon are called "photochromic compounds." BACKGROUND OF THE INVENTION Various types of photochromic compounds have been synthesized and proposed for use in applications that change color or darken in sunlight. In particular, U.S. Patent No. 3,562,172
Spiro(indoline) naphthoxazine compounds, such as those described in U.S. Pat. Such photochromic compounds, whether in crystalline form or as a solution or dispersion in a transparent medium, rapidly change color from a colorless state to blue when exposed to sunlight or ultraviolet light, and in the dark. When left alone or in the absence of strong ultraviolet light, it returns to its original colorless state. DETAILED DESCRIPTION OF THE INVENTION According to the present invention, there is provided a material containing a novel photochromic compound represented by the general formula I below. In the above general formula (1), R1 is selected from the group consisting of CI Cs alkyl, phenyl, phenyl (CI -Ca ) alkyl, allyl, and hepnotic and di-substituted phenyl, and the phenyl substituent is CI C4 alkyl, C, -
C, alkoxy. Preferably R1 is CI Cm alkyl or phenyl or benzyl group. R2 and R3 in formula (1) are each selected from the group consisting of Cr Cs alkyl, phenyl, mono- and di-substituted phenyl, benzyl, or are combined to form 6-8
forms a cyclic ring selected from the group consisting of an alicyclic ring containing 5 carbon atoms (including spiro carbon atoms), norbornyl, and adamantyl. Phenyl substituents can be chosen from CIC4 alkyl and CI-cs alkoxy groups. Preferably, Rz, Rz are each selected from CTCs alkyl. When one of R2 or R3 is a tertiary alkyl group such as tert-butyl or tert-amyl, the other is preferably an alkyl group other than a tertiary alkyl group. Ra and Rs in the general formula ■ are hydrogen and C+, respectively.
Cs selected from the group consisting of alkyl, halogen, C, -C, alkoxy, nitro, cyano, C, -C, alkoxycarbonyl. R4, R5 are the available carbon atoms of the indolino moiety of the compound, i.e. the 4-position or the 5-position or the 6-position.
It can be present in any two positions, position or 7. Preferably, when the substituents R4, R2 are other than hydrogen, these substituents are carbon atoms at positions 4 and 5 or positions 5 and 6 or positions 4 and 7 or positions 6 and 7 of the indolino moiety. Any halogen can be used, i.e. chlorine, bromine, iodine, fluorine, but
Chlorine, bromine, and especially chlorine are preferred. Preferably, R.
R, is hydrogen, C, -C2 alkyl, chlorine, bromine, c, -
selected from the group consisting of CS alkoxy. Of particular interest are those in which R1 is C1-Ct alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, nibutyl, isobutyl, tert-butyl, and each of Rz, Rs is methyl or General formula I is ethyl or phenyl, and each of R4 and R2 is hydrogen or methyl or methoxy or chloro
It is a photochromic compound represented by Photochromic compounds used in the present invention include benzene,
Toluene, chloroform, ethyl acetate, methyl ethyl ketone, acetone, ethyl alcohol, methyl alcohol, acetonitrile, tetrahydrofuran, dioxane,
Can be dissolved in common organic solvents such as methyl ether of ethylene glycol, dimethyl formamide, dimethyl sulfoxide, methyl cellosolve, morpholine, ethylene glycol, and can also be dispersed in liquids including water, alcohol, and other solvents. You can also do it. The amount of solvent used to dissolve the photochromic compound used in the present invention, when applied to the host material,
The amount must be sufficient to provide a photochromic composition that provides photochromic amounts of the compound in the host material. The photochromic compound used in the invention is a colorless or transparent solution prepared from a transparent polymer or a copolymer or blend of such transparent polymers and a suitable organic solvent, such as dissolved in one or more of the 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 solution, polyvinylpyrrolidone/acetonitrile solution, polystyrene/ Contains benzene solution and ethylcellulose/methylene chloride solution. The above photochromic solution or composition is applied to a transparent support such as triacetyl cellulose or polyethylene terephthalate or Baryta paper, and upon drying, the photochromic material is colored blue by ultraviolet radiation and returns to colorless upon removal of the ultraviolet source. can be obtained. The photochromic compounds or compositions containing them for use in the present invention may be applied to or incorporated into solid transparent polymeric organic materials, synthetic plastic host materials. Preferably, the host material is an optically transparent material, e.g. a material suitable for ophthalmic devices such as ophthalmic lenses or windows,
This material is suitable for applications such as windshield glass. Host materials containing photochromic compounds used in the present invention include photochromic plastic films, sheets and lenses, such as lenses for sunglasses, ski goggles,
It can be used in the manufacture of visors, sun visors, camera lenses and filters. As used herein, the term "optical element" is intended to include lenses and transparencies. Examples of transparent host materials that can be used with the photochromic compounds used in this invention include polymers of polyol (allyl carbonate) monomers, polyacrylates, poly(alkyl acrylates) such as polymethyl methacrylate, acetyl cellulose, triacetyl cellulose,
Cellulose acetate propionate, cellulose acetate butyrate, poly (vinyl acetate), poly (vinyl alcohol), polyurethane, polycarbonate, polyethylene terephthalate, polystyrene, poly (styrene-methyl methacrylate) copolymer, poly (styrene-acrylonitrile) copolymer, polyvinyl butyral is included. Transparent copolymers and blends of transparent polymers are also suitable as host materials. Preferably, the host material is a polycarbonate such as poly(4,4'-dioxydiphenol-2,2-propane) sold under the trademark LEXAN; PLEXIGLAS (7
) polymethyl methacrylate such as materials sold under the trademark; polyols (allyl carbonate), especially CR
Diethylene glycol bis(allyl carbonate), sold under the trademark -39, and its copolymers, e.g. with vinyl acetate, e.g.
allyl carbonate) 80-90% and vinyl acetate 10-
Copolymers with 20%, especially diethylene glycol bis(allyl carbonate) 80-85% and vinyl acetate 15
- an optically transparent polymeric organic material made from cellulose acetate, cellulose propionate, cellulose butyrate, polystyrene and its copolymer with methyl methacrylate, vinyl acetate, acrylonitrile, and cellulose acetate butyrate; . Polyol (allyl carbonate) monomers that can be polymerized to form transparent host materials include allyl carbonates of linear or branched aliphatic or aromatic liquid polyols, such as aliphatic glycol bis(allyl carbonate) compounds or alkylidene It is a bisphenol bis(allyl carbonate) compound. These monomers can be referred to as unsaturated polycarbonates of polyols, such as glycols. These monomers are
Methods known in the art, such as U.S. Patent No. 2.370.56
7, No. 2.403.113. Polyol (allyl carbonate) has the general formula % Formula % In the above general formula (1), R is a group derived from an unsaturated alcohol, usually allyl or substituted allyl group,
is a group derived from a polyol, and n is an integer of 2-5, preferably 2. The allyl group R is a halogen, in particular chlorine or bromine, or an alkyl group containing 1-4 carbon atoms in the 2-position;
It may generally be substituted with methyl or ethyl groups. The R group has the general formula % (in the above general formula, Ro is hydrogen, halogen, or C,
-C, which is an alkyl group). Special examples of R include allyl, 2-
Included are chloroallyl, 2-bromoallyl, 2-fluoroallyl, 2-methylallyl, 2-ethylallyl, 2-isopropylallyl, 2-n-propylallyl, and 2-n-butylallyl. Most commonly, R is an allyl group Hz
C=CHCHHz-. R' is a polyvalent group derived from a polyol, which can be an aliphatic or aromatic polyol containing 2 or 3 or 4 or 5 hydroxy groups. Typically, polyols contain two hydroxy groups, ie, glycols or bisphenols. Aliphatic polyols may be linear or branched, and 2-

Contains 0 carbon atoms. Typically, aliphatic polyols are alkylene glycols having 2-4 carbon atoms or poly (Cg C4) alkylene glycols,
Examples include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, and triethylene glycol. The aromatic polyol can be represented by the general formula (2). In the above general formula (1), A is a divalent group derived from an acyclic aliphatic hydrocarbon, such as an alkylene or alkylidene group having 1 to 4 carbon atoms, such as methylene, ethylene, dimethylmethylene (isopropylidene) and R
8 represents a lower alkyl substituent of 1-3 carbon atoms,
p is 0 or 1 or 2 or 3. Preferably the hydroxyl group is in the ortho or para position. Particular examples of R groups include ethylene (-CH2-cHz
-) ,) alkylene groups containing 2-10 carbon atoms 1-CH2-, such as rimethicin, methylethylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, 2-methylhexamethylene, octamethylene, decamethylene; 0-CH, -1CHz CHt
OCHz CHz-1CHHz OCHz CHz
-1CHz CHz-CHz OCHt CHz
Alkylene ether group such as CH2-; -CH2C
H2-O-CH2CH2--O-CH2CH, -1CH
t CHz CH20-CHz CHz CHt O
Alkylene polyether groups such as CHz CHz CHz-, -CH2CH2-O-CO-0-CH, CH,
-1-CH2CH2-0-CH2CH2-0-CO-0
Included are alkylene carbonate and alkylene ether carbonate groups such as -CH2CH2-0-CH2CH2-; and isopropylidene bis(p-phenyl) or H3. Most commonly, R” is -CHt CHz-
or -CHzCHl-0-CH2CH2- or -C
Ht CHz OCHt CHz O-CHz C
Hz-. Specific examples of polyol (allyl carbonate) salts include ethylene glycol bis(2-chloroallyl carbonate), ethylene glycol bis(allyl carbonate), diethylene glycol bis(2-methallyl carbonate), diethylene glycol bis(allyl carbonate) , triethylene glycol bis(allyl carbonate), propylene glycol bis(2-ethylallyl carbonate), 1,3-propanediol bis(allyl carbonate), 1,3-butanediol bis(allyl carbonate), 1,4-butane Diorbis (2)
-bromoallyl carbonate), dipropylene glycol bis(allyl carbonate), trimethylene glycol bis(2-ethylallyl carbonate), pentamethylene glycol bis(allyl carbonate), and isopropylidene bisphenol bis(allyl carbonate). The industrially important polyol bis(allyl carbonate) monomer that can be used in the present invention is CHz=CHC
Hz OCOCHz CHtOCHzCHz O
CHz CHz OC-OCHtCH= CH
t ,, V triethylene glycol bis(oriru carbonate) CHz=CHCHz OCOCHzCHz-0CHz
CHzOCOCHz CH2CHz, V; diethylene glycol bis(allyl carbonate) CH2=CH-CHz-0-C-0-CH2=H! ~0
COCH2CH2CHt ■ 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 process of preparation by phosgenation of and subsequent esterification with allyl alcohol (or polyol), the monomer product may contain a class of related monomers in which the moiety attaching the allyl carbonate group contains one or more carbonate groups. There is sex. One type of these related monomers is represented by the general formula (■). In the above general formula (1), R is as defined above, R is a divalent group derived from a diol, such as alkylene or phenylene, and S is an integer of 2-5. One related monomer of diethylene glycol bis(allyl carbonate) can be represented by the general formula (2). CH2=CHCHz OC(OCH2CH20CHt
CHt OC)s OCHt-CH=CH, [
X In the above general formula (1), S is an integer of 2-5. The polyol (allyl carbonate) 7mer is typically 2-2
0% by weight of a related monomer can be present, such a related monomer can be present as a mixture, ie a mixture of species denoted by S equal to 2, 3.4, etc. Furthermore, partially polymerized forms of polyol (allyl carbonate) heptamers can also be used. In that embodiment, the 7-mer is thickened by heating or a small amount, e.g. 0.5-1.5 parts/100 parts monomer (ph
m) is partially polymerized using an initiator and does not contain a gel;
Gives a more viscous succulent material. Polyol (allyl carbonate) used herein
Seven-termer or a similar name, such as diethylene glycol bis(allyl carbonate), shall mean and include the monomer or prepolymer of that name and one of the related monomers contained therein. The amount of photochromic compound or composition containing the compound applied to or incorporated into the host material is not critical and generally depends on the desired color intensity of the composition and the photochromic compound incorporated or incorporated into the host material upon irradiation. Depends on the method used for application. Typically, the greater the amount of photochromic compound added, the greater the color intensity. Generally, such amounts can be described as photochromic amounts. Normally, the amount of photochromic compound incorporated into the host material is about 0.05% by weight of the host material. O
1 - about 20% by weight, more usually about 0.05 - about 10
% by weight. Stated another way, the amount of photochromic compound used to produce a photochromic effect is typically 6.4516 cal (lin”) on the surface of the host material, regardless of the thickness of the host material article.
About 1 to about 1' Omg of photochromy/reactive compound
is within the range of Thus, photochromic compounds are present in high concentrations in thin samples, films or coatings, and in low concentrations in thick samples. Ethanol solutions of the photochromic compounds of the invention are typically colorless or pale yellow or green or blue. These solutions rapidly change color to purple or blue when exposed to UV light and return to their original color or colorless state when the UV source is removed. Such color changes can be repeated many times. The photochromic compounds or compositions used in the present invention can be applied to or incorporated into host materials by methods known in the art. Such methods 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 (tmbiba
tion), and the incorporation of photochromic compounds as separate layers between adjacent layers of host material. “
The term ``imbibe'' or ``imbibe'' refers to the diffusion of a photochromic compound alone into a host material, solvent-assisted diffusion, absorption of a photochromic compound into a porous polymer, gas phase transfer, and the like. shall mean and include such transfer mechanisms.For example, (81) the photochromic compound or composition used in the present invention is mixed with a polymerizable composition which, when cured, forms an optically clear polymeric host material; The polymerizable composition can be cast as a film, sheet, or lens, or can be formed into a sheet or lens by injection molding or other methods. or other solvent or solvent mixture and then immersing the host material in a bath of such solution or dispersion for a period of minutes to hours, e.g. 2-3 minutes to 2-3 minutes.
It can be absorbed into the solid host material by soaking for a period of time. The bath is normally at an elevated temperature, usually in the range of 50-120°C. The host material is then removed from the bath and dried. (C) The photochromic compounds and compositions are applied to the host material by conventional methods such as spraying, brushing, spin-coating or dipping from a solution or dispersion of the photochromic compound in the presence of a polymeric binder. Can be applied to surfaces. Thereafter, the photochromic compound is absorbed into the host material by heating the host material, for example in a dryer, at a temperature in the range of 80-180<0>C for 1 minute to several hours. (d) In one variation of the above absorption method, the photochromic compound or composition is applied onto a temporary support, such as a piece of kraft paper, aluminum foil, polymer film or cloth, and then a layer of host material is applied. , for example in a dryer. (eJ photochromink compound can be dissolved or dispersed in a transparent polymeric material and applied to the host surface in the form of an adherent film by any suitable method such as spraying, brushing, spin-coating or dipping). (f) Additionally, the photochromic compound can be incorporated or applied to the transparent polymeric material by any of the methods described above and then incorporated into the host material as a separate layer between adjacent layers of the host material. The photochromic compound used in the present invention can be prepared by combining the corresponding t-1-trosohydroxyquinoline compound with the corresponding indoline (Fisher base) or indolium salt (
For example, it can be synthesized by reacting with a compound (eg, iodide). The two precursor materials are refluxed in a suitable solvent such as toluene or isopropanol containing a base such as triethylamine until the reaction is complete. The photochromic compound is recovered from the reaction mixture, for example by filtration, and if necessary by recrystallization to obtain a purer product. The invention will now be further illustrated by examples, which are intended to be illustrative only, as numerous changes and modifications will be apparent to those skilled in the art. Cold Charcoalization (Method A) A suspension of 5-nitroso-6-chiralinol (1.74 g, 0.01 mol) in 73 ml of toluene was heated to 100-108°C with stirring. To this heated suspension were added 2.01 g of triethylamine (0.02 mol) and 0.5 m j! 3,43 g of iodide 1,2.3 suspended in 40 mg of toluene containing ethanol and
．． 5.6-bentamethyl-3-ethylindolium (0
, 01 mol) was added gradually over 15 minutes. The flask containing indolium iodide was 30 m j
! of toluene, and the toluene wash was added to the reactor. After refluxing the mixture in the reactor for 4 hours, the reaction mixture was decanted and evaporated to almost dryness. A mixture of a dark green gum and a small amount of crystalline material was obtained. The almost dry mixture was soaked with 7-8 ml of fresh toluene, filtered and washed twice with 4 ml of toluene. The filtrate and washings were combined and evaporated. The crystalline material gradually became a gum over the course of 5 days. 2-3mm of this thick gum! Soak in ethanol, filter,
Washed with ethanol and air dried. Yellow-green powder (0.81g
)was gotten. The filtrate 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 recrystallized from an acetone:n-hexanol mixture (2:3 v/v). 0.76 g of yellow-green microcrystalline powder was obtained. This was determined by nuclear magnetic resonance (NMR) spectroscopy and elemental analysis.
．． 3.5.6-tetramethyl-3-ethylspiro[indoline-2,3' (3H) pyrido(3,2-f)
(1,4) benzoxazine]. Elemental analysis of a sample of the product from the same reaction components, but from a different production, shows 77, 45% by weight carbon, 6.88% by weight hydrogen.
, nitrogen content was 11.11% by weight. These values almost agree with the theoretical values of 77.60% by weight of carbon, 6.78% by weight of hydrogen, and 11.31% by weight of nitrogen. Method B A suspension of 5-nitroso-6-chiralinol (0.73 g, 0.0042 mol) in 30 ml of Improper Tools was heated to reflux temperature. To this suspension, add 0.85 g (
35 mm containing 0,0085 mol) of triethylamine
! 1.44 g (0,
0042 mol) of 1.2.3°5.6-bentamethyl-3-ethylindolium iodide was added slowly over a period of 15 minutes. The resulting blue reaction mixture was refluxed for 2 hours and then allowed to cool to room temperature. The blue solution was allowed to evaporate overnight and crystals formed within the almost dry solution. The crystals were filtered, washed with approximately 2 ml of isopropanol, and air-dried to form a dark olive green powder (1.32 g).
I got it. This powder was added to 120 ml of boiling n-hexane and the undissolved powder was removed by filtration. Activated carbon (1.5 g) was added to the filtrate, stirred for several minutes, and then filtered. After removing the activated carbon, the volume of the filtrate was reduced to about 40 ml, 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 air-dried. The dried crystals (0.46 g) were identified by NMR as 1.3.5.6-tetramethyl-3-
It was identified as ethylspiro[indoline-2,3°[3H]pyrido[3,2-engine](1,4)benzoxazine]. Other photochromic compounds within the general formula I can be prepared by adding 5-nitroso-6-chiralinol to other indoline or iodine compounds having the substituents listed in Table 1, using toluene as the solvent. It was produced by reacting with indolium chloride. 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. Ethanol solutions of each compound of Examples 1-9 turned blue when irradiated with ultraviolet light at room temperature. These solutions returned to their original hue or colorless after removal of ultraviolet light. A suspension of 5-nitroso-6-chiralinol (1,05 g SO, 006 mol) in 30 mf of toluene was heated to reflux temperature with stirring. Add 20 to this heated solution.
1,37 g 1-butyl- dissolved in ml toluene
3-Methyl-3-ethyl-2-methyleneindoline (0
,006 mol) was added gradually over 20 minutes. After refluxing the mixture in the reactor for 3 hours, the reaction mixture was transferred to an evaporating dish and evaporated to near dryness. 7m7 of this almost dry mixture! of fresh toluene, filtered and washed twice with 3 ml of toluene. The filtrate and washings were combined and evaporated to give a viscous dark blue gum. The resulting gum paste was redissolved in about 20 m6 of diethyl ether, filtered and the filtrate was evaporated in a hood. When one drop of this ether solution was diluted with ethanol and irradiated with ultraviolet light for about 30 seconds at room temperature, the solution turned blue. This blue color disappeared after about 5 minutes when the UV light was removed. The gum paste obtained by evaporating the ether solution was dried in a vacuum desiccator for several days. 1 of this dry paste
Dissolved in 0 mj2 of toluene, dried over 5.6 g of sodium sulfate, filtered and washed with 3 m It of toluene. The filtrate and washings were combined and evaporated in a hood to give a dark blue paste. For human application, 1 part of the photochromic compound of Example 1-10 was mixed with 10 parts of a commercially available lacquer (3M Lacquer N112253) and 1 part of the photochromic compound of Example 1-10.
A spray of 1 part toluene and 10 parts methyl ethyl ketone was added to the lacquer solution. This lacquer solution was prepared from diethylene glycol bis(allyl carbonate).
(fin)X was sprayed onto the surface of a 2mar thick polymer coupon. After drying, the coated coupons were heated in an air dryer at 160° C. for 20 minutes. After cooling, the residual lacquer was removed with adhesive tape and the surface was cleaned with a cloth moistened with acetone. The photochromic sensitivity of this photochromic tablet to activation by artificial sunlight was tested. The results are shown in Table 2. Table 2 mΔTR1%ΔOD, λmax j %, sec 1
76 1.33 572 48 0.
41 143 72 1.13 41
4 66 0, 98 455
0.16 86 - 0.49
18 7 0.61 21B 37
0.29 219 46 0, 40
2610 59 0.67 211
, ΔT, is the % decrease in visible light transmittance induced after 4 minutes of artificial sunlight irradiation (measured using a photopic filter). 2. Δ0D - 58062 caused by 4 minutes of artificial sunlight irradiation
'Change in the saturated optical density measured in the range 3, t + A - after artificial sunlight irradiation, the transmittance of the sample (
Example 12 A prior art photochromic compound was treated in the same manner as described in Example 11 with diethylene glycol bis( Allyl carbonate). The photochromic sensitivity of these articles is shown in Table 3 in comparison to the articles from Example 2.3.4. These photochromic compounds can be represented by the following general formula. In the above general formula, R1, R6, Rh, and X are as shown in Table 3. A suspension of 5-nitroso-6-chiralinol (0.52 g, 0.003 mol) in 20 mβ of toluene was heated to about 100° C. with stirring. To this heated suspension was added 0.60 g of triethylamine (0,006 mol).
containing 2 (1,75 suspended in Jml toluene)
g (0,003 mol) of 1°2-dimethyl-3 iodide
,3-bis(p-methoxyphenyl)indolium,
It was added gradually over about 20 minutes. The mixture in the reactor was kept at about 100° C. for 2.5 hours and the extent of the reaction was monitored by thin layer chromatography (TLC). The reaction was almost complete after 1 hour. After 2.5 hours at about 100°C, a further 0.17 g (0,001 mol) of 5-nitroso-
6-Chiralinol was added to the reactor and approximately 100'
Even after 2 hours at 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 formed in this almost dry paste. The almost dry product was soaked with 7 m It of fresh toluene, filtered and washed slowly with 3 ml of toluene. A large amount of 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 (0.79 g). A sample of this powder was dissolved in ethanol and irradiated with ultraviolet H (366 RUW) for about 30 seconds. The solution turned from light green to blue and returned to light green when the UV light was removed. 35m/! A suspension of 5-nitroso-6-chiralinol (1,39 g, 0.008 mol) in toluene was heated to about 100<0>C with stirring. To this heated suspension was added 1.6 g of triethylamine (0,016 mol) suspended in 35 ml of toluene 2,95
20g of 1,2.5.6-tetramethyl-3,3-spiro(cyclohexyl)-(3H)indolium iodide
- Added gradually over 30 minutes. The progress of the reaction was checked by TLC. The mixture in the reactor was heated to about 100°C.
After a period of time, the reaction mixture (dark brown solution) was evaporated to near dryness. The resulting paste was soaked in 6 ml of fresh toluene for several minutes and filtered to remove insoluble matter.
The resulting solid was washed with 2 ml of toluene. Combine the filtrate and washings and evaporate to a dark brown paste (2.07g)
I got it. Take a small amount (about 1mg) of this paste for about 2-3 minutes.
ml of ethanol and the resulting solution was exposed to UV light (366 runs) at room temperature. The solution turned light blue in color and returned to its original color in about 2 minutes after the UV source was removed. 1.22 g (0,00
7 mol) of 5-nitroso-6-chiralinol, 60 m
1.70 g (0,007 mol) of 1-allyl-3,5,6-1-tumethyl-3-ethyl- in toluene of
The mixture was reacted with 2-methyleneindoline at about 100° C. for about 3 hours. The reaction mixture was evaporated to near dryness and the resulting paste was soaked with 6 ml toluene for several minutes and then filtered. Insoluble matter was washed with 2 ml of toluene. The filtrate and washings were combined and evaporated to give a dark (greenish) brown paste (2.49g). A small amount of this paste was dissolved in 2-3 ml of ethanol and the resulting pale yellow solution was exposed to UV light (366 nm). The solution turned green and returned to its original color approximately 1-2 minutes after the UV light source was removed. 1 in 49 m1 of toluene according to the operation of Otsu Oku Earthworks Example 14.
．． A suspension of 74 g (0,01 mol) of 5-nitroso-6-chiralinol in 40 ml toluene containing 2 g (0,02 mol) of toluene was added to
g (0.01 mol) of 1,3-diethyl-2 iodide
, 3,5,6-titramethylindolium. After 3 hours of reaction, a dark blue-green solution was obtained which was evaporated to almost dryness. 6m of the resulting paste
1 of toluene for several minutes and filtered. The resulting solid was washed with 2 ml of toluene, and the washings were combined with the filtrate. The resulting dark solution was evaporated to yield 3.28 g of dark green paste. A small amount of this paste was prepared for photochromicity by the method of Example 14.
y) test was conducted. The paste was pale green in ethanol solution, but turned deep blue when exposed to ultraviolet light. The solution returned to a light green color in about 3-4 minutes after removing the UV light. Example 17 Following the procedure of Example 14, 1.74 g (0,01
mol) of 5-nitroso-6-chiralinol and 2.57 g
of 1-butyl-2-ethyl-3,5,6-drimethyl-2-methyleneindoline was refluxed in 70 ml of toluene for 3 hours. The resulting product was a dark blue paste. A small ethanol solution of this paste was pale to dark blue, but turned sky blue upon exposure to UV light. The solution returned to its original color after about 5 minutes when the UV light was removed. Following the procedure of Major Earthwork Example 14, 1.22 g of 5-nitroso-6-chiralinol was suspended in 50 ml of hot toluene. Into this suspension, 'l Q m jl! 1,70 g of 1-butyl-3,3°5.6- diluted with toluene
Tetramethyl-2-methyleneindoline was added slowly over about 10 minutes. The resulting mixture was refluxed for 3 hours. An ethanolic solution of the resulting product turns dark blue when exposed to UV light, and when the UV light is removed it turns about 4-
After 5 minutes, the original hue returned. The above operation was repeated using isopropanol as a solvent. The product was a very dark green paste. Fischer base 1-benzyl-2,5,6-drimethyl-3-ethyl-
The procedure of Example 18 was followed except that 2-methyleneindoline was used. The resulting ethanolic solution of the product is pale green in color and turns medium blue upon exposure to ultraviolet light;
When the ultraviolet light was removed, the original color returned to its original color after about 3-4 minutes. 0.89 g (0,005
mol) of 5-nitroso-6-chiralinol,
1,32 g dissolved in 25 ml isopropanol
(0,005 mol) of 1. 3. 5. 6-Tetramethyl-3-phenyl-2-methyleneindoline was added slowly and the reaction mixture was refluxed for 1 hour. The resulting dark blue reaction solution was evaporated overnight to yield a dark blue (almost black) colored gum. Further evaporation produced a hard cake and considerable decomposition. After chromatography of this gum on a thin layer chromatography plate, the photochromicity of the product was confirmed in a silica gel matrix. A summary of the compounds of Examples 17-20 is shown in Table 4. +L-, ,L +L,i = E.U. While the invention has been described in particular detail with respect to several embodiments thereof, such details do not fall within the scope of the claims. Nothing other than the extent should be construed as limiting the scope of the invention.

Claims (9)

[Claims] (1) The following general formula ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ [In the above general formula, (a) R_1 is C_1-C_5 alkyl, phenyl, phenyl (C_1-C_4) alkyl, allyl, and mono- and di-substituted phenyl. (b) R_2 and R_3 are each C_1-C_5 alkyl, phenyl, C_1-
C_4 alkyl, and C_1-C_5 alkoxymono and di-substituted phenyl, benzyl, or an alicyclic ring containing 6-8 carbon atoms (including spiro carbon atoms) in combination, norbornyl, adamantyl (c) R_4 and R_5 each are hydrogen, C_1-
A solid transparent polymeric organic host material containing a photochromic amount of a photochromic compound selected from the group consisting of C_5 alkyl, halogen, C_1-C_5 alkoxy, nitro, cyano, C_1-C_6 alkoxycarbonyl. (2) The transparent host material is essentially a polymer of polyol (allyl carbonate), a copolymer of polyol (allyl carbonate) and vinyl acetate, polyacrylate, poly(alkyl acrylate), acetylcellulose, triacetylcellulose, acetic acid. selected from the group consisting of cellulose propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), polycarbonate, polystyrene, poly(styrene-methyl methacrylate) copolymer, poly(styrene-acrylonitrile) copolymer, polyvinyl butyral The material described in claim No. (1). (3) A material according to claim (2), wherein the transparent host material is selected from poly[diethylene glycol bis(allyl carbonate)] and its copolymer with vinyl acetate. (4) Photochromic compounds have the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the above general formula, (a) R_1 is selected from the group consisting of C_1-C_4 alkyl, allyl phenyl, benzyl, (b) R_2 and R_3 are each C_1-C_5
selected from alkyl, (c) each of R_4 and R_5 is hydrogen, C_1-
selected from the group consisting of C_2 alkyl, chlorine, bromine, C_1-C_5 alkoxy] The material according to claim (2). (5) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the above general formula, (a) R_1 is selected from the group consisting of C_1-C_4 alkyl, phenyl, and benzyl, (b) Each of R_2 and R_3 is C_1-C_5
selected from alkyl, (c) each of R_4 and R_5 is hydrogen, C_1-
selected from the group consisting of C_2 alkyl, chlorine, bromine, C_1-C_5 alkoxy] Polycarbonate containing a photochromic amount of a photochromic compound represented by copolymers selected from the group consisting of polymethyl methacrylate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene, poly(styrene-methyl methacrylate) copolymers, poly(styrene-acrylonitrile) copolymers. Materials described in scope item (1). (6) A material according to claim (5) in which the photochromic compound is present in an amount of 0.05-10% by weight. (7) The host material is poly[diethylene glycol bis(
6. A material according to claim 6, which is selected from the group consisting of allyl carbonate) and its copolymers with vinyl acetate. (8) The material according to claim (7), wherein R_1, R_2, R_4, R_5 are methyl and R_3 is selected from methyl and ethyl. (9) Copolymer is diethylene glycol bis(allyl carbonate) 80-90% and vinyl acetate 10-20%
The material according to claim (7), which is a copolymer with.