DE19834940A1 - New photochromic spiro compounds used with preferably polythiourethane matrix in phototropic glass, preferably for ophthalmologic applications, and optical measuring, recording and storage matrix are e.g. spiro(fluorene-pyrrolophthalazines) - Google Patents

Abstract

Photochromic substituted spiro(fluoren-9,1'-pyrrolo(2,1-a)phthalazine and (2,1-a)isoquinoline) and analogues (I) are new. Photochromic substituted spiro(fluoren-9,1'-pyrrolo(2,1-a)phthalazine and (2,1-a)isoquinoline) and analogues of formula (I) are new: R1 = 1-4 carbon (C) alkyl, cyclohexyloxycarbonyl, acyl derived from 1-4 C aliphatic or aromatic carboxylic acids or cyano (CN); R2 = hydrogen (H) or as R1; R3 = a group completing a dibenzocyclopentadiene, monobenzodiphenylcyclopentadiene, tetraphenylcyclopentadiene or dibenzocyclohexa-2,5-dien-4-one ring; R4 = H or 1-4 C alkyl; R5 = H, 1-4 C alkyl or 1-4 C alkoxy; R6 = H; or R5R6 = a condensed benzene ring; X = nitrogen (N), methylene (CH2) or C-R7; R7 = H or 1-4 C alkyl; or R4R7 = a condensed benzene ring; Y = C-R8; R8 = H, 1-4 C alkyl, phenyl, 1-4 C phenylalkyl or styryl; or Y = N if R4R7 and R5R6 = condensed benzene rings; Z = C linked to X by a double bond or CH if X is CH2. The full definitions are given in the DEFINITIONS (Full Definitions) Field. An Independent claim is also included for polymer matrices, comprising polythiourethanes (II) obtained by reacting diisocyanate(s) (A) selected from 2,5-bis(isocyanatomethyl)norbornane (A1), dicyclohexylmethane 4,4'-diisocyanate (A3), isophorone diisocyanate (A4) and 1,3-bis(isocyanatomethyl)cyclohexane (A5) with polythiols (B) selected from pentaerythrityl tetrakis-3-mercaptopropionate (B0) and 1,2-bis-(2-mercaptothioether)-3-mercaptopropane (B3).

Description

The present invention relates to new photochromic compounds for installation in Polymer matrices, improved polymer matrices with a high refractive index that facilitate the incorporation of these Allow photochromic compounds, as well as phototropic glasses such. B. for ophthalmic Applications and optical storage matrices based on such photochromic Compounds and polymer matrices.

Photochromic substances have a variety of uses due to their sensitivity to light possible applications. The possibility to switch between two states light-induced and Bleaching thermally (or photochemically) is used. So glasses materials, Actinometer [H. Dürr, H. Bouas-Laurent, Photochromism Molecules and Systems, Elsevier, Amsterdam 1990], Systems for Information and Data Storage [U. P. Wild, C. Bräuchle in, H. Dürr and H. Bouas-Laurent, s. 930-75] as well as switchable enzymes [J. Willner, S. Rubin, F. Effenberger, J. Bäuerle, J. Wonner, J. Am. Chem. Soc. 1992, 114, 3150-51] become.

Great progress has been made in recent years, particularly in the field of sun protection, especially for ophthalmic applications of photochromic systems. The quite photostable spiroxazines [NY Chu, DE OS 33 10 388 (2), American Optical Corp., Southbridge, Man. (USA)] are produced as particularly stable substances. With these substances, the commercially usable photochromic (phototropic) plastic glass Transitions® could be developed and brought onto the market. These glasses have refractive indices on the order of n _D ²⁰ = 1.5-1.6.

Photochromic substances are drawn onto the plastic matrix (e.g. DE 35 16 568, US 4300821 or US 4578305). The corresponding plastic matrix is based on one Polydiethylene glycol bisallyl carbonate. The disadvantage is that the subsequent coloring with photochromic molecules often lead to poor adhesion and poor light stability.

An object of the present invention was to provide new photosensitive (photochromic) substances that are suitable for incorporation into suitable polymer matrices. A Another task was to develop improved polymer matrices that have a high Have refractive index and allow the incorporation of photochromic compounds. Besides Another task was to use phototropic glasses e.g. B. for ophthalmic applications and optical storage matrices based on such photochromic compounds and To provide polymer matrices.

The present application relates to photochromic compounds of the general formula (I)

in which mean:
R ₁ = C _1-4 alkoxycarbonyl, cyclohexyloxycarbonyl, acyl, derived from aliphatic carboxylic acids with 1-4 C atoms or from aromatic carboxylic acids, or CN;
R ₂ = H or a radical as defined for R ₁ ;
R ₃ = a radical to complete an optionally substituted dibenzocyclopentadiene, monobenzodiphenylcyclopentadiene, tetraphenylcyclopentadiene or di benzocyclohexa-2,5-dien-4-one ring;
R ₄ = H or C _1-4 alkyl,
R ₅ = H, C _1-4 alkyl or C _1-4 alkoxy;
R ₆ = H;
or R ₅ and R ₆ together form a fused benzene ring;
X = N, CH ₂ , or CR ₇ ,
wherein R ₇ = H or C _1-4 alkyl;
or R ₄ and R ₇ together with R _{4 form} a fused-on benzene ring;
Y = CR ₈ ,
where R ₈ = H or C _1-4 alkyl, phenyl, C _1-4 phenylalkyl, such as. B. benzyl, or styryl, especially β-styryl,
or N if R ₄ together with R ₇ and R ₅ together with R ₆ each form a fused-on benzene ring;
Z = a carbon atom bonded to X with double bond or CH in the case where X = CH ₂ ;
wherein phenyl groups contained in R ₃ and R ₈ with up to five substituents, preferably with one or two substituents, in particular in the 4- or 3,5-position, and fused-on benzene rings with up to four substituents, preferably with one or two substituents, in particular can be substituted in the 2- or 2,3-position, which are independently selected from the group consisting of halogen, in particular chlorine, bromine and iodine, nitro, CN, C _1-4 alkyl, C _1-4 - Alkoxy, C _1-4 alkoxycarbonyl and C _1-4 acyl.

These compounds according to the invention are suitable for incorporation into suitable polymer matrices. You can therefore for the production of phototropic glasses such. B. for ophthalmic Applications and optical storage matrices can be used.

A preferred radical R ₃ is generally a radical for completing an optionally substituted dibenzocyclopentadiene (fluorene), ie a substituted, in particular substituted in the 2,7-position, biphenylene group.

Is preferably selected as the substituents R ₁ and R _{2 is} C _1-4 alkoxycarbonyl, C _1-4 acyl groups or CN-groups.

Appropriate representatives of the photochromic compounds of the general formula (I) are the pyrrolophthalazines of the general formula (II), in which Z is a carbon atom bonded to X with a double bond, and the tetrahydroindolizines of the general formula (III), in which X = CH ₂ and Z = CH. The meaning of the other substituents and groups is as stated above.

In the case of pyrrolophthalazines (II), compounds of the general formula (IV) have proven to be particularly expedient, in which X = N and Y = CR ₈ . These pyrrolophthalazines are stable and have a particularly pronounced photochromism with only slight self-coloring. Particular embodiments for the compounds of the general formula (IV) are given under numbers 1 and 2 in Table 1.

In the case of tetrahydroindolizines (III), compounds of the general formula (V) have proven particularly expedient, in which Y = CR ₈ . These tetrahydroindolizines are characterized by a very low intrinsic color and nevertheless have good photochromism. Particular embodiments for the compound of the general formula (V) are given under numbers 3, 4, 5 and 6 in Table 1.

When exposed to light, the photochromic compounds of the general formula (I) are subject to a ring opening and form the color form of the general formula (I *), which undergoes 1,5-electocyclization under thermal or photochemical influence with the regression of the photochromic compound (I) (see, for B. DE 32 20 257 C2).

Since the photochromic compounds (I), whether as a solid pure substance, are dissolved in solvents or embedded in matrices, always contain a certain proportion of the color form (I *) the protection claimed in relation to the photochromic compounds (I) should also always extend to the appropriate color form (I *).

The synthesis of the photochromic compounds is exemplified in the reaction scheme 1 in the case where R ₅ and R _{6 represent} a fused-on benzene ring (see, for example, DE 32 20 257 C2).

Reaction scheme 1

In the event that C _1-4 alkoxycarbonyl, cyclohexyloxycarbonyl or acyl groups have been selected for R ₁ and R ₂ , first the spirocyclopropene (VII), which was obtained photochemically from the compound (VI), is added with the equivalent amount of a base (VIII), e.g. B. a phthalazine or tetrahydroindolizine derivative, dissolved in absolute diethyl ether and stirred for two days with the exclusion of light and moisture at room temperature. The crystals formed after this time are suctioned off. In this way, colorless to yellowish crystals of the compounds of the general formula (I) are obtained.

As spirocyclopropene (VII) z. B. fluorene spirocyclopropene diesters are used, wherein the alkyl groups contained in the ester groups methyl, ethyl, propyl, isopropyl and Tertiary butyl, cyclohexyl or enhexyl can be. The fluorene spirocyclopropene can continue to be halogenated. For example, chlorine, bromine, iodine or fluorine can be in the 2 position of the fluorene residue be introduced. Halogen atoms such as chlorine and bromine or nitro can be in the 2-7 position be introduced.

The pyrrolophthalazine compounds number 1 (Table 1) are obtained by reacting the Spirocyclopropenes (VII) with phthalazine derivatives (VIII), which are commercially available or can be synthesized according to usual regulations. The tetrahydroindolizine of Numbers 3, 4 and 6 (Table 1) are by the implementation of suitable bases of the general  Formula (VIII) prepared. So z. B. 1-phenyl, 1-cyanophenyl, 1-nitrophenyl, 1-benzyl, 1-Styryl-, 1-parachlorostyryl-, 1-paranitrosytryl- and 3,4-dihydroisoquinoline as corresponding Base components are used. Analogously, paracyano, paranitro and phenyl 3,4-dihydroisoquinoline can be used as the base component. The styryl-substituted 3,4- Dihydroisoquinolines can also carry alkoxy radicals such as methoxy groups.

In the event that R ₁ and R _{2 are} each CN, appropriately substituted dicyan-spiropyrazoles (VI) and bases of the general formula (VIII), for. B. phthalazine or tetrahydroindolizine derivatives, dissolved in absolute diethyl ether and exposed in a photolysis apparatus with Pyrex filter (125 watt Hg high pressure lamp). After an irradiation time of about 50 minutes, the starting compounds are used up. After concentration of the reaction mixture in vacuo and separation by column chromatography (SiO ₂ / CH ₂ Cl ₂ ), colorless or yellowish crystals of the corresponding photochromic compounds (I) are obtained.

Following this route, the compounds of numbers 2 and 5 (Table 1) can be synthesized. Dicyan-spiropyrazoles (VI) are used as starting compounds. In the case of a biphenylene group as radical R ₃ , this can be substituted as described.

The spiropyrazoles (VI) are prepared according to the procedures known in the literature. In the case of a biphenylene group as R ₃ , 9-fluorenone is reacted with hydrazine and 9-fluorene hydrazone is obtained, which is oxidized to 9-diazofluorene in a further step using manganese dioxide. In a last step, derivatives of acetylenedicarboxylic acid, in particular ester or cyano derivatives, which are commercially available or were produced according to the known regulations, react with 9-diazoflorene to give the spiropyrazole compounds (VI). If R ₃ is a brominated or chlorinated, preferably in the 2,7-position substituted biphenyl group, 9-fluorenone is first halogenated with N-bromosuccinimide (NBS) or N-chlorosuccinimide (NCS).

In this way, the compounds described in Table 1 were obtained. In addition to the schematic representation, the color and (if measurable) the _half- life τ _{1/2 of} the 1,5-electrocyclization in methylene chloride solution (c = 10 ^-4 to 10 ^-5 mol / l.) For the color forms (IV * or V *) ) specified. This value indicates the time after which the extinction of the color molding solution has dropped to half of its initial value.

Polythiourethanes are suitable as polymer matrices for the incorporation of photochromic compounds known.

Polythiourethanes are produced by adding polythiols (B component) to diisocyanates (A component). Due to the adjustable degrees of crosslinking, chain lengths of the thiols (thioalcohols) and the nature of the diiso cyanates, polythiourethanes can have a broad spectrum of properties ("method for making tailormade plastics" [Houben-Weyl, Methods of Organic Chemistry, Vol. XIV, Thieme Verlag, Stuttgart , 1984, 58]). Suitable A and B components are

Polythiourethanes consisting of the components m-xylene diisocyanate (A ₀ ) and pentaerythritol tetrakis-3-mercaptopropionate (PEMP) (B ₀ ) have hitherto been used in the commercially available plastic glasses from Rodenstock under the name "KI 1.6". They have refractive indices in the range of n _D ²⁰ = 1.6.

In order to achieve a higher refractive index and thus improved wearing comfort by reducing the weight of the glasses and to achieve improved brightening kinetics, attempts were made to add or replace components (A ₁ -A ₅ , B ₁ -B ₁₀ ) in the AI 1.6- Modify polymer. The polythiourethane matrix was synthesized from the A and B components in a manner known per se [EP 043506 A2, Haya Corporation, Tokyo (JP)].

In order to be suitable for ophthalmic applications in the form of self-tinting lenses, the plastic must have high mechanical stability. It should be as shatterproof as possible be and not scratch. All of these requirements are met by the invention Polymer matrices met.

According to the invention, polymer matrices based on polythiourethane, based on EP 0235743 A1, which are suitable for ophthalmic use, were produced with refractive indices n _D ²⁰ ≧ 1.6. These polythiourethanes are obtainable by reacting the above-mentioned diisocyanates A ₁ , A ₃ , A _4, A ₅ and mixtures thereof, with the above-mentioned polythiols B ₀ , B ₃ and mixtures thereof.

It turned out that the following component combinations are particularly preferred in order to enable a high refractive index and at the same time the incorporation of the photochromic compounds (I): A ₁ / A ₃ / B ₀ , A ₁ / A ₃ / B ₃ , A ₄ / A ₅ / B ₃ and A ₃ / A ₅ / B ₃ . With these component combinations it was possible to synthesize matrices with which rapid bleaching after irradiation is possible. The molar ratio of components A _x to A _y can in principle vary from about 5% to 95% to about 95% to 5%. A and B components should provide essentially stoichiometrically equivalent amounts of mutually reactive functional groups, in order to ensure complete curing.

With the particularly preferred combination A ₁ / A ₃ / B ₃ (A ₁ / A ₃ = 75/25 mol% to 95/5 mol%, in particular about 85/15 mol%), it was possible, after incorporation of photochromic substances, to lighten the kinetics as in to achieve commercial glasses.

The above-mentioned polymer matrices are suitable for the production of phototropic glasses and optical storage matrices.

After incorporation of substance 2a (2.00 mg), a T ₀ value of 82%, a T _s value of 11% and a τ ₈₀ value of 0.5 min were obtained. The values of DIN standards 5033 and 58216 regarding suitability at dusk and at night were met. By incorporating a combination of pyrrolophthalazines and tetrahydroindolizines, an optically appealing brown tone was obtained in the matrix.

In addition, the particularly preferred component combination A ₁ / A ₃ / B ₃ (85/15/100 mol%) has a refractive index of close to 1.70 due to the increased thiol and thioether content and is thus above the values achieved so far for commercial glasses (maximum 1.60) .

Fig. 1 shows the refractive index of the combination of components A ₁ / A ₃ / B ₃ (85/15/100 mol%) as a function of the incident wavelength (λ = 260 to 900 nm).

In the case that components A ₁ , A ₃ and B ₃ are used for the polymer matrix, a phototropic glass is produced as follows:

A mixture of the diisocyanates A ₁ and A ₃ is mixed with the polythiol B ₃ . The photochromic compound and a UV stabilizer, preferably 4-methoxybenzophenone, are added proportionally to this mixture. Dibutyl tin dichloride is added as a catalyst for the polyaddition and the mixture is degassed in a high vacuum with constant stirring. This mixture is poured into plastic molds optionally provided with a release agent and left in a desiccator for 20 hours at 4 ° C. and for a further 24 hours at room temperature. In a subsequent temperature program by gradually heating to 50 ° C - 2 hours, 80 ° C - 2 hours, 100 ° C - 1 hour, 110 ° C - 10 minutes, the polythiourethane is cured. The resulting blank is transparent and, depending on the photochromic substances mixed in, shows a weak yellow color or no color.

The plastic blanks obtained in this way are UV / VIS spectroscopic, in particular in the case of λ = 550 nm measured. After exposure with a UV-VIS light source is used for the polymer the color and the fading curve of the photochromic compound.

Fig. 2 generally shows an Ausbleichkurve for a dye in the polymer matrix, taken at λ = 550 nm, wherein:
T ₀ : The T ₀ value indicates the transmission of the photochromic polymer sample before exposure.
T _S : The T _S value indicates the transmission of the polymer sample after 2 minutes of exposure at 23 ° C (standard lamp: Colormatic / UV demonstrator (125 W), Rodenstock).
T ₆₀ : The T ₆₀ value indicates the transmission of the exposed polymer sample after 1 h.
Δ OD: The stroke (Δ OD) indicates the difference between the T _S and the T ₀ value.
τ ₈₀ : The τ ₈₀ value is the time (in minutes) after irradiation of the sample at which the transmission has reached 80% of the stroke.

Table 2a shows the composition of the photochromic polythiourethane matrices, as well as the Amounts of photochromic compounds used.

Table 2b shows the results of the lightening kinetics of the phototropic polymers.

The matrices thus obtained show a very high level in the case of the pyrrolophthalazinyl compounds slight pre-coloring. The tetrahydroindolizines are colorless in the polymer matrix and reach high color depths, especially for CN derivatives.

It is now possible for the first time to produce phototropic plastic glasses with suitable pyrrolophthalazines and tetrahydroindolizines as phototropic dyes in high-index matrices for ophthalmic applications based on polythiourethane. With suitable moles külmischungen the photochromic compounds of numbers 1 to 6, mixed tones z. B. gray, green and brown tones are generated.

The photostability of the photochromic polythiourethane matrices numbers 4, 12 and 18 was investigated in a Sun test device from Heräus (1.8 kW xenon lamp, 290 mm filter, illuminance 600-650 W / cm ² , temperature 35-40 ° C) . After the specified times, the samples were removed, cooled to room temperature and the transmission (Ts) after 5 minutes of UV radiation (Colormatic / UV demonstrator, from Rodenstock) was measured.

As the studies in Table 3 show, the Ts values decrease after an initial one Magnification to an almost constant value. The corresponding PTU glasses therefore have after approximately 50 hours of irradiation, there is only a slight drop in the stroke.

Table 3

Ts values of samples 4, 12 and 18

Production of the photochromic compounds

example 1

1 ', 10b'-dihydro-2', 3'-dimethoxycarbonyl-spiro [2,7-dibromofluoren-9,1'-pyrrolo [2.1-a] phthalazine] (1f)

The synthesis of the educt 2,7-dibromo-2 ', 3'-dimethoxycarbonyl-spiro [fluorene-9,1'-cyclopropene] was carried out according to the method known in the literature. The phthalazine was purchased from Aldrich. To prepare compound 1f, 470 mg (1.0 mmol) of 2,7-dibromo-2 ', 3'-dimethoxycarbonyl-spiro [fluorene-9,1'-cyclopropene] and 130 mg (1.0 mmol) of phthalazine were placed in a 100 ml flask dissolved in 50 ml of absolute diethyl ether and stirred for 2 days with the exclusion of light at room temperature. The crystals formed were suctioned off; there was no need for recrystallization. The product obtained was 330 mg (5.8 × 10 ^-4 mol) of yellow crystals on 1f.

Example 2

1 ', 10b'-dihydro-2', 3'-dicyan-spiro [fluorene-9,1'-pyrrolo [2.1-a] phthalazine] (2a)

The synthesis of the educt 4 ', 5'-dicyan-spiro [fluorene-9,3' - (3H) -pyrazole] was carried out according to the method known in the literature. The phthalazine was purchased from Aldrich. To prepare compound 2a, 536 mg (2.0 mmol) of 4 ', 5'-dicyano-spiro [fluorene-9,3' - (3H) -pyrazole] and 520 mg (4.0 mmol) of phthalazine in 500 were obtained in a photolysis apparatus with Pyrex filter ml of absolute diethyl ether dissolved. The solution was then irradiated with a high-pressure mercury lamp (125 W) for 50 min. After concentrating the solvent, the reaction mixture was purified by column chromatography (SiO ₂ / CH ₂ Cl ₂ ). The product obtained 390 mg (1.05 mmol) of yellow crystals on 2a.

Example 3

1 ', 10b'-dihydro-2', 3'-dicyan-6 ', 10b'-diphenyl-spiro [2,7-dichlorofluorene-9,1'-pyrrolo [2.1-a] phthalazine] (2c)

The synthesis of the educt 2,7-dichloro-4 ', 5'-dicyan-spiro [fluorene-9,3' - (3H) -pyrazole] and 1,4-diphenylphthalazine was carried out according to the methods known in the literature. To prepare compound 2c, 170 mg (0.5 mmol) of 2,7-dichloro-4 ', 5'-dicyano-spiro [fluorene-9,3' - (3H) -pyrazole] and 282 mg ( 1.0 mmol) of 1,4-diphenylphthalazine dissolved in 300 ml of absolute diethyl ether. The solution was then irradiated with a high-pressure mercury lamp (125 W) for 20 min. After concentrating the solvent, the reaction mixture was purified by column chromatography (SiO ₂ / CH ₂ Cl ₂ ). The product obtained 40 mg (6.76 × 10 ^-5 mol) of yellow crystals on 2c.

Example 4

1 ', 5', 6 ', 10b'-tetrahydro-2', 3'-dimethoxycarbonyl-10b'-phenyl-spiro- [fluorene-9,1'-pyrrolo [2,1-a] isoquinoline] (3a) {Reference example}

The synthesis of the starting materials 2 ', 3'-dimethoxycarbonyl-spiro [fluorene-9,1'-cyclopropene] and 1-phenyl-3,4-dihydroisoquinoline were carried out according to the methods known in the literature. To prepare compound 3a, 500 mg (1.63 mmol) of 2 ', 3'-dimethoxycarbonyl spiro [fluorene-9,1'-cyclopropene] and 338 mg (1.63 mmol) of 1-phenyl-3,4-dihydroisoquinoline in 80 ml of absolute Implemented diethyl ether. The course of the reaction was checked by TLC. After the reaction was complete, the solvent was removed in vacuo and the crude product was purified by column chromatography (SiO ₂ / CH ₂ Cl ₂ ). After recrystallization from ether, 610 mg (1.2 mmol) of colorless crystals of 3a were obtained.

Example 5

1 ', 5', 6 ', 10b'-tetrahydro-2', 3'-dimethoxycarbonyl-10b '- (p-methylbenzyl) - spiro [fluoren-9,1'-pyrrolo [2,1-a] isoquinoline] (4b)

The synthesis of the starting materials 2 ', 3'-dimethoxycarbonyl-spiro [fluorene-9,1'-cyclopropene] and 1- (p-methylbenzyl) -3,4-dihydroisoquinoline were carried out according to the methods known in the literature. To prepare compound 4b, a solution of 353 mg is added dropwise to a solution of 460 mg (1.5 mmol) of 2 ', 3'-dimethoxycarbonyl-spiro [fluorene-9,1'-cyclopropene] in 50 ml of absolute diethyl ether with stirring at room temperature (1.5 mmol) 1- (4-methylbenzyl) -3,4-dihydrisoquinoline in 30 ml of absolute diethyl ether. After stirring for 24 hours with the exclusion of light at room temperature, the crystallized precipitate was filtered off with suction. After a subsequent purification by column chromatography (SiO ₂ / CH ₂ Cl ₂ ) and recrystallization from diethyl ether, 510 mg (1.0 mmol) of colorless crystals of 4b were obtained.

Example 6

1 ', 5', 6 ', 10b'-tetrahydro-2', 3'-dicyan-10b '- (p-cyanophenyl) -spiro [fluorene-9,1'-pyrrolo [2.1-a] isoquinoline] (5a )

The synthesis of the starting materials 4 ', 5'-dicyan-spiro [fluorene-9,3' - (3H) -pyrazole] and 1- (p-cyanophenyl) - 3,4-dihydro-isoquinoline was carried out according to the methods known in the literature Methods carried out. To prepare the dicyan-THI 5a, 268 mg (1.0 mmol) 4 ', 5'-dicyan-spiro [fluorene-9,3' - (3H) -pyrazole] and 280 mg (1.2 mmol ) 1- (4-cyanophenyl) -4,5-dihydro-isoquinoline dissolved in 300 ml of absolute diethyl ether and flushed with dry nitrogen for 15 min to remove the dissolved oxygen. The reaction mixture was then irradiated for 20-30 min using a high-pressure mercury lamp (125 W). Nitrogen released indicates the start of the reaction; sales were checked by TLC. After the photolysis was complete, the solvent was concentrated and the crude product was purified by column chromatography (SiO ₂ / CH ₂ Cl ₂ ). The product obtained was 200 mg (0.4 mmol) of white crystals on 5a.

Example 7

1 ', 5', 6 ', 10b'-tetrahydro-2', 3'-dicyan-10b'-phenyl-spiro (2,7-dichlorofluorene-9,1'-pyrrolo [2.1-a] isoquinoline] ( 5d)

The synthesis of the educt 2,7-dichloro-4 ', 5'-dicyan-spiro (fluoren-9,3' - (3H) -pyrazole] and 1-phenyl-3,4-dihydroisoquinoline was carried out according to those known in the literature In order to prepare compound 5d, 320 mg (0.95 mmol) of 2,7-dichloro-4 ', 5'-dicyan-spiro [fluorene-9,3' - (3H) -pyrazole] and. Were used in a photolysis apparatus with Pyrex filter 40 mg (1.9 mmol) of 1-phenyl-3,4-dihydroisoquinoline were dissolved in 500 ml of absolute diethyl ether, the solution was then irradiated for 60 min with a high-pressure mercury lamp (125 W) and the reaction solution was then stirred at room temperature for three days with the exclusion of light After the solvent had been concentrated, the reaction mixture was purified by column chromatography (SiO ₂ / CH ₂ Cl ₂ ) with exclusion of light and recrystallized from diethyl ether, giving 190 mg (3.7 × 10 ^-4 mol) of yellow-white crystals of 5d.

Example 8

1 ', 5', 6 ', 10b'-tetrahydro-2', 3'-dicyan-10b '- (p-chlorophenyl) -spiro [2,7-dibromofluoren-9,1'-pyrrolo [2.1-a] isoquinoline] (5j)

The synthesis of the educt 2,7-dibromo-4 ', 5'-dicyan-spiro [fluorene-9,3' - (3H) -pyrazole] and 1- (p-chlorophenyl) -3,4-dihydroisoquinoline was carried out according to the methods known in the literature. To prepare compound 5j, 600 mg (1.4 mmol) of 2,7-dibromo-4 ', 5'-dicyan-spiro [fluorene-9,3' - (3H) -pyrazole] and 250 mg ( 1.0 mmol) of 1- (p-chlorophenyl) -3,4-dihydroisoquinoline dissolved in 500 ml of absolute diethyl ether. The solution was then irradiated with a high-pressure mercury lamp (125 W) for 30 min. The reaction solution was then stirred at room temperature for one day with the exclusion of light. After concentrating the solvent, the reaction mixture was purified by column chromatography (SiO ₂ / CH ₂ Cl ₂ ) with the exclusion of light and recrystallized from diethyl ether. The product obtained was 70 mg (1.08 × 10 ^-4 mol) of yellow-white crystals of 5j.

Example 9

1 ', 5', 6 ', 10b'-tetrahydro-8', 9'-dimethoxy-2 ', 3'-dimethoxycarbonyl-10b'- (p-chlorostyryl) -spiro [2,7-dibromofluorene-9.1 '-pyrrolo [2,1-a] isoquinoline] (6a)

The synthesis of the starting materials 2 ', 3'-dimethoxycarbonyl-spiro [fluorene-9,1'-cyclopropene] and 1- (p-chlorostyryl) -6,7-dimethoxy-3,4-dihydroisoquinoline were according to those known in the literature Methods carried out. To prepare the compound 6 g, 36 mg (1.0 mmol) of HCl salt of 1- (p-chlorostyryl) -6,7-dimethoxy-3,4-dihydroisoquinoline in 30 ml of absolute diethyl ether was added to 10 mg (1.0 mmol) of triethylamine added dropwise in 10 ml of absolute diethyl ether. After stirring for 15 minutes, 464 mg (1.0 mmol) of 2 ', 3'-dimethoxycarbonyl-spiro [fluorene-9,1'-cyclopropene] were added. After stirring for 24 hours with the exclusion of light at room temperature, the crystallized precipitate was filtered off with suction. Subsequent purification by column chromatography (SiO ₂ / CH ₂ Cl ₂ ) and recrystallization from diethyl ether gave 371 mg (0.5 mmol) of colorless crystals of 6a.

Production of the photochromic polymer matrices

Components A ₁ , A ₃ and B ₃ listed in the following examples were obtained from Rodenstock, A ₄ from Bayer and B ₀ , A ₅ , 4-methoxybenzophenone and diisobutyltin dichloride from Aldrich.

Example 10 Sample No. 2

3.56 g (17.3 mmol) of diisoyanate A ₁ are mixed with 0.78 g (03.0 mmol) of A ₃ and 3.51 g (13.5 mmol) of trithiol B ₃ as well as 3 mg (8.1 × 10 ^-6 mol) of compound 2a and 15 mg (7.1 × 10 ^-5 mol) of the UV stabilizer 4-methoxybenzophenone mixed at room temperature. After adding 0.5 mg (1.6 mmol) of the catalyst diisobutylditin chloride dissolved in dichloromethane, degassing is carried out for 3 hours in a high vacuum with constant stirring. The polymer mixture is poured into plastic molds and left in the desiccator for 20 hours at 4 ° C. and for a further 24 hours at room temperature. The subsequent temperature program provides for gradual heating to 50 ° C (2 h), 80 ° C (2 h), 100 ° C (1 h) and 110 ° C (10 min). The blank obtained (diameter 5.2 cm) is transparent and shows an intense yellow pre-coloring. After exposure to a UV lamp, the matrix turns blue.

Example 11 Sample N ° 7

3.56 g (17.3 mmol) of diisoyanate A ₁ are mixed with 0.78 g (03.0 mmol) of A ₃ and 3.51 lg (13.5 mmol) of trithiol B ₃ as well as 3 mg (4.7 × 10 ^-6 mol) of compound 4b and 15 mg (7.1 × 10 ^-5 mol) of the UV stabilizer 4-methoxybenzophenone mixed at room temperature. After addition of 0.5 mg (1.6 mmol) of the diisobutylditin chloride catalyst dissolved in dichloromethane, the process is carried out as described in Example 10. The blank thus obtained (diameter 5.2 cm) is transparent and shows an orange pre-coloring. After exposure to a UV lamp, the matrix becomes permanently orange (suitability as an optical storage medium).

Example 12 Sample N ° 21

3.56 g (17.3 mmol) of the diisocyanate A ₁ are mixed with 0.78 g (03.0 mmol) of A ₃ and 3.51 g (13.5 mmol) of the trithiol B ₃ and 3 mg (4.3 × 10 ^-6 mol) of the compound 5m and 15 mg (7.1 × 10 ^-5 mol) of the UV stabilizer 4-methoxybenzophenone mixed at room temperature. After addition of 0.5 mg (1.6 mmol) of the diisobutylditin chloride catalyst dissolved in dichloromethane, the process is carried out as described in Example 10. The blank thus obtained (diameter 5.2 cm) is transparent and shows no pre-coloring. After exposure to a UV lamp, the matrix turns turquoise.

Example 13 Sample No. 4

3.56 g (17.3 mmol) of the diisocyanate A ₁ are mixed with 0.78 g (03.0 mmol) of A ₃ and 3.51 g (13.5 mmol) of the trithiol B ₃ and 2 mg (3.4 × 10 ^-6 mol) of the compound 2c at room temperature. After addition of 0.5 mg (1.6 mmol) of the diisobutylditin chloride catalyst dissolved in dichloromethane, the process is carried out as described in Example 10. The blank thus obtained (diameter 5.2 cm) is transparent and shows a yellow pre-coloring. After exposure to a UV lamp, the matrix turns green.

Example 14 Sample N ° 18

3.56 g (17.3 mmol) of the diisocyanate A ₁ are mixed with 0.78 g (03.0 mmol) of A ₃ and 3.51 g (13.5 mmol) of the trithiol B ₃ and 2.3 mg (3.6 × 10 ^-6 mol) of the compound 5j at room temperature. After addition of 0.5 mg (1.6 mmol) of the diisobutylditin chloride catalyst dissolved in dichloromethane, the process is carried out as described in Example 10. The blank thus obtained (diameter 5.2 cm) is transparent and shows no pre-coloring. After exposure to a UV lamp, the matrix turns blue-green.

Claims (12)

1. Photochromic compounds of the general formula (I)
in which mean:
R ₁ = C _1-4 alkoxycarbonyl, cyclohexyloxycarbonyl, acyl, derived from aliphatic carboxylic acids with 1-4 C atoms or from aromatic carboxylic acids, or CN;
R ₂ = H or a radical as defined for R ₁ ;
R ₃ = a radical to complete an optionally substituted dibenzocyclopentadiene, monobenzodiphenylcyclopentadiene, tetraphenylcyclopentadiene or di benzocyclohexa-2,5-dien-4-one ring;
R ₄ = H or C _1-4 alkyl;
R ₅ = H, C _1-4 alkyl or C _1-4 alkoxy;
R ₆ = H;
or R ₅ and R ₆ together form a fused-on benzene ring;
X = N, CH ₂ or CR ₇ ,
wherein R ₇ = H or C _1-4 alkyl;
or R ₄ and R ₇ together with R _{4 form} a fused-on benzene ring;
Y = CR ₈ ,
where R ₈ = H or C _1-4 alkyl, phenyl, C _1-4 phenylalkyl, such as. B. benzyl, or styryl, especially β-styryl, or N, if R ₄ together with R ₇ and R ₅ together with R ₆ each form a fused benzene ring;
Z = a carbon atom bonded to X with double bond or CH in the case where X = CH ₂ ;
wherein phenyl groups contained in R ₃ and R ₈ with up to five substituents, preferably with one or two substituents, in particular in the 4- or 3,5-position, and fused-on benzene rings with up to four substituents, preferably with one or two substituents, in particular in the 2- or 2,3-position, which are independently selected from the group consisting of halogen, in particular chlorine, bromine and iodine, nitro, CN, C _1-4 alkyl, C _1-4 - Alkoxy, C _1-4 alkoxycarbonyl and C _1-4 acyl. 2. Use of the photochromic compounds according to claim 1 for installation in Polymer matrices. 3. Use according to claim 2 for the production of phototropic glasses, in particular for ophthalmic applications. 4. Use according to claim 2 or 3 for the production of optical storage matrices. 5. Polymer matrices comprising polythiourethanes which can be obtained by reacting diisocyanates from the group consisting of 2,5-bis (isocyanatomethyl) norbonane (A ₁ ), dicyclohexyl methane-4,4'-diisocyanate (A ₃ ), isophorone diisocyanate (A ₁ ), 1,3-bis (isocyanatomethl) cyclohexane (A ₅ ) and mixtures thereof, with polythiols from the group consisting of pentaerythritol tetrakis-3-mercaptopropionate (B ₀ ), 1,2-bis (2-mercaptothioether) -3-mercaptopropan (B ₃ ) and mixtures thereof. 6. Polymer matrices according to claim 5 with a combination of components selected from A ₁ / A ₃ / B ₀ , A ₁ / A ₃ / B ₃ , A ₄ / A ₅ / B ₃ and A ₃ / A ₅ / B ₃ , wherein the Molar ratio of the respective diisocyanate components varies from about 5% to 95% to about 95% to 5%. 7. polymer matrices according to claim 6 with the component combination A ₁ / A ₃ / B ₃ and a molar ratio A ₁ / A ₃ of 75/25 mol% to 95/5 mol%, in particular about 85/15 mol%. 8. Use of the polymer matrices according to one of claims 5-7 for the production phototropic glasses, in particular for ophthalmic applications. 9. Use of the polymer matrices according to one of claims 5-7 for the production of optical  Storage matrices. 10. Phototropic glasses comprising one or more photochromic compounds of the general Formula (I) according to claim 1 and a polymer matrix according to any one of claims 5-7. 11. Use of the phototropic glasses according to claim 10 as an ophthalmic Glasses material. 12. Use of the phototropic glasses according to claim 10 as optical storage matrices, for. B. for measurement, recording and storage purposes.