DE19741705A1 - Photochromic indeno(2,1-f)naphtho(1,2-b)pyran compounds useful e.g. in photochromic spectacle lenses - Google Patents

Abstract

Photochromic indeno(2,1-f)naphtho(1,2-b)pyran derivatives (I) are new. The derivatives are of formula (I). R1, R2 = 1-2 substituents selected from a group E; E = 1-6 carbon (C) alkyl, 1-6 C alkoxy, chloro (Cl) or fluoro (F) or a 5-6 C cycloalkyl, phenyl, benzyl, di-(1-6 C)-alkylamino, dicyclohexylamino, diphenylamino, piperidyl, morpholinyl or pyridyl group; or 2 R1 groups and/or 2 R2 groups = a group completing a benzo, pyrido, pyrazino, pyrimidino, furano or thiopheno ring; m, n = 0, 1 or 2; R4 = G; monochloro- or monofluoro-phenyl; naphthyl, optionally mono-substituted by Cl, F, 1-6 C alkyl or 1-6 C alkoxy; phenanthryl; pyrenyl; (iso)quinolyl, (di)benzofuranyl, (di)benzothienyl, carbazolyl or indolyl attached to the naphthopyran system by a carbocycle; phenyl di- or tri-substituted by Cl, F, 1-6 C alkyl, 1-6 C alkoxy or by a 1-6 C w-phenylalkyl, or 1-6 C w-phenoxyalkyl group, in which the w-phenyl ring may be the X, X' or R4 group of another photochromic pyran system; G = hydrogen (H); hydroxyl (OH); 1-6 C alkyl; 5-6 C cycloalkyl; 1-6 C acyl; 1-6 C alkoxy; a phenyl or benzyl group, optionally mono-substituted by 1-6 C alkyl or 1-6 C alkoxy; Cl; F; X, X' = Z; Z = (a) optionally mono-, di- or tri-substituted phenyl or naphthyl or (b) optionally mono-, di- or tri-substituted pyridyl, furanyl, benzofuran-2- or -3-yl, thienyl, benzothien-2- or -3-yl, in which the substituted are selected from OH, amino, mono- and di-(1-6 C)-alkylamino, piperidino, morpholino, pyrryl, R, Cl and F; (c) R or 3-6 C cycloalkyl, optionally mono-substituted by 1-6 C-alkoxy, Cl or F; R = 1-6 C alkyl, 1-6 C chloroalkyl, 1-6 C fluoroalkyl, 1-6 C alkoxy or mono-(1-6 C)-alkoxy-(1-4 C)-alkyl; or CXX' = saturated 5-10 C monocyclic, 7-12 C bicyclic or 7-12 C tricyclic hydrocarbon ring or fluoren-9-ylidene; or either X or X' = mono- or di-substituted phenyl, substituted in the p-position by phenyl, -(CH2)p-phenyl or -O-(CH2)p-O-phenyl, in which the second phenyl ring is part of a second, not necessarily identical, photochromic diarylpyran; p = 1-6; Y = H, 1-6 C alkyl, 1-6 C acyl or a benzoyl or naphthoyl group, optionally mono-substituted by 1-6 C alkyl or 1-6 C alkoxy; with the proviso that R<1>, R<2> not = E if R4 = G and X, X' = Z.

Description

The invention relates to photochromic compounds (sterically sophisticated fused naphthopyrans).  

1st reaction sequence

In the following, reference is made to the attached as Figs. 1 and 2 and overwritten with synthesis route drawings, to which also refer to the reference numerals used below.

The substituted or unsubstituted ones used as starting material Benzo or naphthophenones A are either commercially available or can easily and mostly in good by Friedel-Crafts acylation according to 1 Yields are obtained.

The second step is a Stobbe condensation using amber produced diester according to 2 of the half ester B. If the two over The keto group-linked rings are not identical, creating an iso merengemisch. Notwithstanding the illustration in WO 96/14596 further worked with the mixture of isomers. The separation of honey gene, usually non-crystallizing isomers is very expensive, they can on the synthetic route chosen according to the invention later very simple be performed.

The half-ester mixture is isomerized with aqueous alkali according to 3 saponified mixture of diacids C.

By heating with acetyl chloride is dehydrated according to 4 the isomer mixture of the cyclic anhydrides D prepared.

According to FIG. 5, aluminum chloride is converted by intramolecular 5-ring Cyclization synthesized the isomer E mixture. These connections  crystallize very well and in most cases, thanks to their under different solubility in benzene easily separated into the two isomers become.

The desired isomer is formed under the influence of Acetanhy by intramolecular 6-ring cyclization according to 6 of esters F. Die This is then alkaline according to 7 to the hydroxy-flourenone derivative G saponified.

The reaction with a 2-propyn-1-ol derivative according to 8 leads to the weakly photochromic, strongly dark red colored indenone-annellated Naphthopyrans H. This reaction is not described in detail here, since they are carried out analogously to the 1- or 2-naphthols let ren. Examples of this can be found u. a. in US 5,066,818, US 5,238,981 and EU 0246 114.

With corresponding Grignard compounds, the Ver Compounds J. Their free hydroxyl group can still according to 10 to the Class K are derivatized.

The radicals mentioned in the formula images of FIGS . 1 and 2 mean:
R ₁ and R ₂
are independently 1 to 2 (m, n = 0, 1, 2) substituents from the group F, which consists of C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, chloro or flouro or from a group consisting of C ₅ -C ₆ cycloalkyl, phenyl, benzyl, dialkyl (C ₁ -C ₆ ) amino, dicyclohexylamino, diphenyl amino, piperidyl, morpholinyl or pyridyl
or two R ₁ and / or two R ₂ independently form together a carbo- or heterocyclic ring from the group of benzo, pyrido, pyrazino, pyrimidino, furano and thiopheno.

R ₄ is a substituent from group G consisting of hydrogen, hydroxy, C ₁ -C ₆ alkyl, C ₅ -C ₆ cycloalkyl, C ₁ -C ₆ acyl, C ₁ -C ₆ alkoxy, phenyl, benzyl, monosubstituted phenyl monosubstituted benzyl, chloro and fluoro, wherein the aryl substituents are C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy;
or it is monochloro- or monofluoro- substituted phenyl, unsubstituted or monosubstituted naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, or indolyl; wherein the heterocycles are connected via the carbocycle with the Naphthopyransystem and the substituents from the group chloro, fluoro, C ₁ -C ₆ al kyl or C ₁ -C ₆ alkoxy come;
or it is di- or trisubstituted phenyl, wherein the substituents from the group chloro, fluoro, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ ω-phenylalkyl or C ₁ -C ₆ -phenoxyalkyl removed become. The ω-permanent phenyl ring can in turn represent the X, X 'or R ₄ radical of another photochromic pyrans system.

X and X 'either belong to the group Z, ie they are independent of each other

• a) the unsubstituted, mono-, di- and trisubstituted aryl groups phenyl and naphthyl,  
• b) the unsubstituted, mono-, di- and trisubstituted heterocyclic groups pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl and benzothien-3-yl, wherein the substituents in a) and b) a group consisting of hydroxy, amino, mono (C ₁ -C ₆ ) alkylamino, di (C ₁ -C ₆ ) alkylamino, piperidino, morpholino, pyrryl, (C ₁ -C ₆ ) alkyl, ( C ₁ -C ₆ ) chloroalkyl, (C ₁ -C ₆ ) fluoroalkyl, (C ₁ -C ₆ ) alkoxy, mono (C ₁ -C ₆ ) alkoxy (C ₁ -C ₄ ) alkyl, chloro and fluoro be , were taken,
• c) (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) chloroalkyl, (C ₁ -C ₆ ) fluoroalkyl, mono (C ₁ -C ₆ ) alkoxy (C ₁ -C ₄ ) alkyl, (C ₃ C ₆ ) cycloalkyl, mono (C ₁ -C ₆ ) alkoxy (C ₃ -C ₆ ) cycloalkyl, chloro (C ₃ -C ₆ ) cycloalkyl and fluoro (C ₃ -C ₆ ) cycloalkyl selected

or together with the carbon atom of the point of attachment, they form a saturated C ₅ with the pyran

-C ₁₀

monocyclic, C ₇

-C ₁₂

bicyclic or C ₇

-C ₁₂

tricyclic hydrocarbon ring or fluorene-9-ylidene;
or X or X 'is mono- or disubstituted phenyl which is in p-position for linking with -phenyl, - (CH ₂

) _p

Phenyl or -O- (CH ₂

) _p

-O-phenyl sub is substituted (p = 1, 2, 3 ..., 6).

The second phenyl ring can be a second - not necessary as identical - include photochromic diarylpyran.  

Y is selected from the group consisting of hydrogen, (C ₁ -C ₆₎ alkyl, (C ₁ - C ₆₎ acyl, unsubstituted benzene, unsubstituted naphthoyl, mono-substituted benzoyl and naphthoyl mo nosubstituiertem been taken out, said aryl substituents C ₁ - C ₆ alkyl or C ₁ -C ₆ alkoxy.

The above with the proviso that R ₁ and R ₂ does not belong to the group F when R _{4 has been} taken from group G and X and X 'belong to group Z.

The above-mentioned synthetic route has opposite to that in WO 96/14596 recommended way to different advantages.

Various compounds can not be represented on the path described in WO 96/1. The route described according to the invention is considerably gentler, for example the one-hour heating with concentrated phosphoric acid to above 190 ° C. is omitted. As a result, sub-substituents R ₁ and R ₂ also more sensitive groups can be used. The closure of the 5-ring in front of the 6-ring also often leads to products that are difficult or impossible to represent in the way mentioned in WO 96/14596 - closure of the 6-ring in front of the 5-ring. Even with the same target product, eg. As in the case of symmetrical benzophenones as starting material, Weni ger by-products, simpler cleaning and higher yields are waiting for it on the way described according to the invention.

The exact synthetic approach is in the illustration of the examples described by way of example.  

2. Special features of the invention claimed molecule structures

The following special variations can be individually or used in combination.

a) Benzene-fused naphthopyrans

The use of naphtho instead of benzophenones leads to surprise the way to longer wavelength absorbing compounds, both in the ge closed (not stimulated) as well as in the open (stimulated) form.

The marked bathochromic shift and the drastic increase in the Absorption coefficient of the longest wavelength absorption band of ge closed form is not expected for the expert, since the fused naphthyl ring due to electronic decoupling (Ver twisting of the two ring systems by steric hindrance of the H atoms as in the fused phenyl ring) at most a small inductive Ef should exercise. The longest wavelength absorption will continue through the naphthopyran and not caused by the naphthalene system. There the spectral irradiance of the sun on the earth 's surface Range 360-410 nm to longer wavelengths to 2.88 times rises (EN 1836, Table C.1), this effect is just for use in photochromic lenses of particular importance.

Equally surprising is the bathochromic shift in absorption the open form. Molecules with this structural unit already absorb far into the red spectral range of visible light, the color impression is therefore green. With the connections according to the state of  Technology, by contrast, only the shorter-wave part of the spectrum can be covered, the color impression is orange to blue / gray (page 2, line 25 of WO 96/14596).

Table 1: Absorption maxima of the open and closed forms

example

The first four compounds correspond to the prior art (WO 96/14596), the production of V1 and V2 are described there explicitly.  

The substitution sites of R ₁ , R ₂ and R ₃ are shown in the formula for Table 2, R ₄ is hydrogen in all cases.

The preparation of the test specimens and the measuring methodology is in the Bei play described.

FIGS. 3 and 4 show the absorption of the closed mold and the absorption of the open mold, the latter has been normalized for better recognition of the bathochromic shift of about the same absorption intensity.

b) Compounds with several photochromic color centers

Although these ring-annulated naphthopyrans due to their molecule structure already has a lower migration behavior than ordinary ones Naphthopyrans (e.g., U.S. 5,369,158), this may be modified by Ver Double the molecular weight can be further reduced.

This is possible in two ways. About the component X or X ', as be already shown in WO 96/01884 or via a suitable partner R.

For example, if 1,2-bis (4-bromophenyl) ethane or 1,2-bis (4-bromo phenoxy) methane reacted on both sides to Grignard and with two Equivalent naphthopyrans of the structure H implemented, it is formed symmetrical double molecule. However, it is also possible to have an ent correspondingly substituted photochromic compound of other structure For example, a spirooxazine or a shorter wavelength absorbing  Naphthopyran to convert to Grignard and with the naphthopyrans the structure H to implement novel compounds. If you choose this second photochromic compound so that their absorption maximum just falls into the "absorption hole" around 470 nm, we obtain in one Molecular structure very dull, almost neutral colors (gray-brown). The Advantages of such compounds are already in DE 43 21 487 be wrote.

By doubling over the substituent X or X 'and subsequent doubling again over a bifunctional Grignard are Tetra- Systems with molecular weights over 2000 accessible.

c) Fast naphthopyrans

Already known from WO 96/14596 systems had the goal faster brightening than previous 2H-naphthopyrans. Exemplary as radicals R in position 13 only alkyl groups described. Erfindungsge It has been recognized that with the use of sterically demanding aromatic residues have a significant and unexpected increase in uptake bright speed is connected. At the same time, the formation of Fulvenes, which in α-hydrogen-bearing alkyl groups under Wasserab can arise, made impossible. This deep colored destruction products can u. a. arise during the life test (xenon light).

The replacement of alkyl with phenyl already brings this stability advantage. The faster lightening, however, only when replaced by bulkier Aryl groups clearly. The introduction of o-substituents in the phenylrin ge at X or X 'leads, as described in US 5,066,818, to a strong Slowing down the whitening speed. The introduction of  Substituents in the phenyl radical R in position 13, however, leads überra Schenderweise to the opposite, to an increase in Aufhellgeschwindig ness.

Particularly preferred are poly-substituted phenyl radicals or those analogous aryl radicals such as 1- or 2-naphthyl, 9-phenanthryl, pyrenyl and over the carbocycle bound to the skeleton heteroaromatics, such as Benzofuranyl, benzothienyl, quinolyl or isoquinolyl.

This effect is all the more surprising because in the alkyl series introduction increasingly bulky residues has no recognizable effect, as in the WO 96/14596 on page 33 can be seen.

R ₄ Whitening speed T½ in sec. -CH ₃ 362 -CH ₂ -CH ₃ 237 -CH (CH ₃ ) ₂ 264 -C (CH ₃ ) ₃ 313 R ₁ = R ₂ = CH ₃ ; R ₃ = OCH ₃

Table 2: Whitening kinetics at 23 ° C and 40 ° C Example Δ (10 min, 23 ° C) T ½ (40 ° C)

• a) R ₁ = OCH ₃ ; R ₂ = R ₃ = H;
  
• b) R ₁ = R ₃ = OCH ₃ ; R ₂ = H;
  
• c) R ₁ = R ₂ = H; R ₃ = OCH _3;
  

Examples V3, V4 and V5 as well as 4, 5, 11 and 12 correspond to the prior art; the representation of V3, V4 and V5 is explicitly described in WO 96/14596,
Δ = relative lightening within 10 min at 23 ° C
= 100% (τ10min-τs) / (τo-τs)
τs is the transmission reached after 15 minutes of darkening
τo is the transmission in the fully brightened condition
τ10min is the transmission after 10 min lightening in the dark
T1 / 2 = time to brighten half of the darkening (half-life)

EXAMPLE 1

i) Aluminum chloride (40 g) is dissolved in a 1 liter flask which is well-hydrated in an ice-bath Is cooled, suspended in about 400 ml of dichloromethane with stirring. to closing one slowly pours molten 2 Naphthoyl chloride (50 g, melting point 50 ° C) and allowed to the mixture (continue in ice bath) stir for 5 min. Then drip a mixture of anisole (27 g) and 50 ml of dichloromethane and the reaction mixture is allowed to sit Thaw stirring overnight. The next day the mixture is submerged Stir on 200 g of ice / 500 ml of water. It is stirred for 10 min and then separates the organic phase in a separating funnel. This will be two extracted with water and dried over sodium sulfate. After Abde styling of the solvent crystallizes the residual oil in the standing glass sen. After recrystallization from about 500 ml of boiling methanol colorless crystals (58 g), which were analyzed by NMR spectroscopy as 2- (4) Methoxybenzoyl) naphthalene were identified.

ii) Tert.Butanol is pre-melted in a warm water bath. potassium tert-butylate (30 g) is dissolved in 600 ml of tert-butanol in a 1 liter three-necked flask suspended and the above reaction product and succinimides added (45 g). The mixture is stirred well and refluxed for 1 h heated. Thereafter, potassium tert-butylate (30 g) and Bern are again added dimethyl stearate (45 g) and allowed to reflux for 2 h. After cooling, it is hydrolyzed with a total of 2 l of water. Under Stirring is done with conc. Hydrochloric acid acidified. Subsequently, twice extracted with 400 ml of diethyl ether and the combined ether phases who washed once with 400 ml of water. Then twice with 500 ml saturated sodium bicarbonate solution extracted. It works  Product as a carboxylate in the aqueous phase, once with 200 ml of ether washed and then stirred in a large beaker with conc. Hydrochloric acid is acidified. Subsequently, twice with each Extracted 400 ml of ether and the organic phase once ge with water to wash. After drying over sodium sulfate, the ether is removed thoroughly rotates. The orange-yellow honey-like reaction product (80 g) was analyzed by means of NMR spectrum as 3-methoxycarbonyl-4- (4-methoxyphenyl) -4- (2-naph ethyl) -3-butenoic acid.

iii) In a 1 liter flask, the above reaction product is in a solution of potassium hydroxide (40 g) dissolved in about 600 ml of water. The educated brown reaction solution is heated under reflux for 3 h. After the Ab Cool with stirring and good cooling in an ice bath with conc. hydrochloric acid acidified. The mixture is then extracted twice with 400 ml of ethyl acetate. The combined ethyl acetate phases are washed once with water and after drying over sodium sulfate, thoroughly spun off. The honey-like Reaction product (75 g) was analyzed by NMR spectrum as 3-carboxy-4- (4-meth oxyphenyl) -4- (2-naphthyl) -3-butenoic acid.

iv) The above reaction product is treated with acetyl chloride (35 g) in 300 ml of Es Dissolved acetic acid. While stirring is then heated under reflux for 2 h. To Distilling off the solvent, the residue is still warm in about 600 ml Dissolved ethyl acetate and extracted twice with water. Subsequently, will extracted twice with 300 ml of 5% sodium carbonate solution. The or ganic phase is washed again with water, over sodium sulfate dried and thoroughly spun off. The reaction product (65 g) falls as dark viscous oil and was analyzed by NMR spectrum as (4- Methoxyphenyl-2-naphthyl-methylene) succinic anhydride identified.  

v) The above reaction product is added in about 600 ml of dichloromethane Room temperature dissolved and then cooled well in an ice bath. to closing is aluminum with good stirring and cooling in portions Add chloride (35 g) and allow the mixture to thaw overnight. Thereafter, the reaction mixture for hydrolysis in 1 liter of ice / water ge poured. After separating the organic phase, this is twice with each Washed 500 ml of water and then twice with 600 ml 5% Sodium hydroxide extracted. After washing the combined aqueous-alkaline Phases with 250 ml of ether is acidified with conc. Hydrochloric acid with stirring It is extracted twice with 400 ml of ethyl acetate and the organic Washed with water, dried over sodium sulfate and basified abge spun. It remains behind a brown solid residue (45 g), with NMR spectrum as 3- (4-methoxyphenyl) -6,7-benzindenone-2-acetic acid was identified. The same with the reaction theoretically resulting isomer 6-methoxy-3- (2-naphthyl) -indenone-2-acetic acid could not be detected.

vi) The above reaction product will suspend in about 300 ml of acetic anhydride diert. After addition of sodium acetate (20 g), the mixture is allowed to stand for 3 hours Stirring heated to reflux. The product precipitates when cooled. After cooling to room temperature (and briefly in the fridge) is the formed soft crystalline orange-brownish precipitate is sucked off and washed with a little acetic anhydride until the filtrate is no longer dark runs off brown. Then it is washed thoroughly with water and at Dried 60 ° C. The product (bright orange solid, 30 g) was determined by NMR spectrum as 1 l-acetoxy-9-methoxy-dibenzo [a, g] fluo ren-13-on identified.  

vii) The above reaction product is suspended in 400 ml of ethanol and washed with Potassium hydroxide (25 g). The reaction mixture is 1.5 h under Stirring heated to reflux, gradually forming a magnificent tiefgrü ne color can be observed. After cooling, about half of the etha nols and the remaining residue together with 1 liter of water heated on the hot plate until a deep green solution has formed. Then the solution is removed from the hot plate and still hot under stirring ren with conc. Hydrochloric acid acidified. The result is a umbrabraune Sus pension, which is cooled with stirring to room temperature. The Sus pension is sucked off and washed thoroughly with water. The abge Nutsche fabric is still very muddy and will be as good as possible at the Diaphragm pump sucked dry. After drying at 60 ° C this was Browarbene product (25 g) by NMR spectrum as 1 l-hydroxy-9-meth oxy-dibenzo [a, g] fluorene-13-one identified.

viii) 3 g of the above reaction product are taken together with 4- Methoxybenzophenoacetylide (4 g, prepared from 4-methoxybenzophenone and sodium acetylide) in about 300 ml of toluene. After adding a Spatula tip 4-toluenesulfonic acid, the reaction mixture for 1.5 h under Reflux heated. In the course of the reaction, the first is poorly soluble Naphthol starting material more and more in solution; It creates a reddish brown Mi research. After a brief cooling, the toluene is evaporated in vacuo and the residue is dissolved in 40 ml of dichloromethane and a column chromatography graphite with alumina (water content 3%) as stationary and dichloro methane / hexane mixture (2: 1) as the mobile phase. To final After cleaning the crude product is digested in about 100 ml of methanol and slightly warmed. After cooling, the resulting suspension is removed sucked, washed with methanol and dried. The dark product (3 g)  was determined by NMR spectrum as 6-methoxy-3 - (- 4-methoxyphenyl) -3-phe nyl-15-oxo-benzindeno [2,1-f] naphtho [1,2-b] pyran identified.

ix) 1 g of the above reaction product is dissolved in 50 ml of absolute THF The mixture is dissolved and cooled in an ice bath. You give as long as lithium aluminum Add small portions of the anhydride until the color of the reaction solution no longer lightening up. The mixture is stirred for 10 min and poured into water acidifies with conc. Hydrochloric acid until the phases are clear and separate the organic phase. After extraction with water, drying over Na triumsulfat and evaporating off the solvent leaves a brownish viscous Residue, which crystallizes by addition of methanol. You stir the Suspension for a few minutes at room temperature and then sucks the Precipitation. The slightly brownish solid (0.8 g) was analyzed by NMR. Spectrum as 6-methoxy-3- (4-methoxyphenyl) -3-phenyl-15-hydroxy benzindeno [2,1-f] naphtho [1,2-b] pyran identified. In solution as well as in the glass is to observe green photochromism.

EXAMPLE 2

The procedure is analogous to Example 1, only in step ix) are 1 g of the reaction product from step viii) in 50 ml of absolute THF Room temperature dissolved with stirring. To this solution are added 2 equi added valent Phenylmagnesiumchlorid solution and the whole at Room temperature stirred for 1 h. Then it is poured into water, acidified with conc. Hydrochloric acid until the phases are clear and separates the organic phase. After extraction with water, drying over sodium umsulfat and evaporation of the solvent leaves a dark brown oil, which crystallized by the addition of methanol. The suspension is stirred for a few minutes at room temperature and then sucks the low  knock off. The beige solid (0.7 g) was analyzed by NMR as 6-methoxy-3 - (- 4-methoxyphenyl) -3,15-diphenyl-15-hydroxy benzindeno [2,1-f] naphtho (1,2-b] pyran identified.

EXAMPLE 3

The steps i) to vi) of this example were based on the J. Chem. 1958, p. 986 by F.G. Baddar, L.S.El-Assal and V..Baghos published article with some modifications.

i) to vi) Analogously to Example 1 step ii) with 4-methoxybenzophenone (50 g) as Starting material. The result is 3-methoxycarbonyl-4- (4-methoxyphenyl) -4-phe nyl-3-butenoic acid (75 g), which analogously to Example 1 steps iii) to v) on to a mixture of 3- (4-methoxyphenyl) -indenone-2-acetic acid and 6- Methoxy-3-phenyl-indenone-2-acetic acid is processed. The isomers Separation is possible by hot digestion in benzene. After cooling and The suspension is filtered off with suction to give, as residue, pure 3- (4- Methoxyphenyl) indene-2-acetic acid as orange-yellow crystals (25 g), the was identified by NMR spectrum. This was analogous to Example 1 Steps vi) to vii) converted to 5-hydroxy-3-methoxy-7H-benzo [c] fluoren-7-one (20 g), which was obtained as a red-violet powder and by NMR spectrum was identified.

vii) Analogously to Example 1 step viii) with 3 h heating at 100 ° C instead of refluxing There is 6-methoxy-3- (4-methoxyphenyl) -3-phenyl-13-oxo-indeno [2,1-f] naphtho [1,2-b] pyran as a dark red solid (3 g), which by NMR Spectrum was identified.  

viii) The analogous reaction to Example 1 step ix) with the above product provides 6-methoxy-3- (4-methoxyphenyl) -3-phenyl-13-hydroxy-indeno [2,1-f] naph thol [1,2-b] pyran (beige powder, 0.7 g), which by NMR spectrum was identified.

EXAMPLE 4

The procedure is analogous to Example 3, only in step viii) are 1 g of the reaction product from step vii) in 50 ml of absolute THF under stirring solved. To this solution are added 2 equivalents of butylmagnesium chloride The solution was added and stirred at room temperature for 1 h. Then it is poured into water, acidified with conc. Hydrochloric acid on, until the phases are clear and separates the organic phase. After Extrak tion with water, drying over sodium sulfate and evaporation of the solvent leaves a dark brown oil, the addition of methanol crystal lisiert. If the product does not crystallize, stir in an ice bath until Crystals fail. The suspension is stirred in for a few minutes Room temperature, then sucks the precipitate and washed with metha nol after. The resulting brownish solid (0.5 g) was analyzed by NMR. Spectrum as 6-methoxy-3- (4-methoxyphenyl) -3-phenyl-13-butyl-13-hy droxy-indeno [2,1-f] naphtho [1,2-b] pyran identified.

EXAMPLES 5-9

The procedure is analogous to Example 4, only instead butylmagnesiumchlo chloride
in example 5 phenylmagnesium chloride,
in example 6 1-naphthylmagnesium bromide,
in example 7 2-methylphenylmagnesium bromide,
in Example 8 2,5-Dimethylphenylmagnesiumbromid and
in Example 9, 9-phenanthrylmagnesium bromide.

The products (mostly beige powder) were analyzed by NMR spectroscopy than the ones substituted on the C-13 with the corresponding Grignard residue Methoxy-3- (4-methoxyphenyl) -3-phenyl-13-hydroxy-indeno [2,1-f] naph tho [1,2-b] pyrane identified.

EXAMPLE 10

The procedure is analogous to Example 3, only in step vii) takes place Reaction with 4,4'-dimethoxybenzophenoacetylid instead of 4- Methoxybenzophenonacetylid. It is heated at 60 ° C for 2 h. There is 6 Methoxy-3,3-bis (4-methoxyphenyl) -13-xo-indeno [2,1-f] -naphto [1,2-b] -pyran as a dark red solid (3 g) identified by NMR spectrum has been. This is reacted analogously to Example 1 step viii) and it arises 6-methoxy-3,3-bis (4-methoxyphenyl) -13-hydroxy-indeno [2,1-f] naphtho [1,2-b] pyran (0.6 g) as a brownish solid identi by NMR spectrum identi was fiked.

EXAMPLE 11

The procedure is analogous to Example 4, only with 6-methoxy-3,3-bis (4-methoxy phenyl) -13-oxo-indeno [2,1-f] naphtho [1,2-b] pyran as starting material material instead of 6-methoxy-3- (4-methoxyphenyl) -3-phenyl-13-oxo indeno (2,1-f] naphtho (1,2-b] pyran to give 6-methoxy-3,3-bis (4-meth oxyphenyl) -13-butyl-13-hydroxyindeno [2,1-f] naphtho [1,2-b] pyran (0.6 g) as a brownish solid identified by NMR spectrum.  

EXAMPLES 12-14

The procedure is analogous to Example 11, but instead of butylmagnesium chloride
in example 12 phenylmagnesium chloride,
in Example 13 1-Naphthylmagnesiumbromid and
Example 14 2-methylphenylmagnesium bromide.

The products (mostly beige powder) were analyzed by NMR spectroscopy than the ones substituted on the C-13 with the corresponding Grignard residue Methoxy-3,3-bis (4-methoxyphenyl) 13-hydroxy-indeno [2,1-f] naphtho [1,2-b] pyrans identified.

EXAMPLE 15

The procedure is analogous to Example 1 steps ii) to ix), but in Step ii) with benzophenone as starting material, in step viii) with 4,4'- Dimethoxybenzophenone acetylide instead of 4-methoxybenzophenone acetylide and in step ix) with phenylmagnesium chloride solution (analogously to Example 2) Lithium aluminum hydride. The brownish solid obtained is 3,3-bis (4-meth oxyphenyl) -13-hydroxy-13-phenyl-indeno [2,1-f] naphtho (1,2-b] pyran (0.6 g), which was identified by NMR spectrum.

EXAMPLE 16

The procedure is analogous to Example 15 with 2.5- Dimethylphenylmagnesium bromide instead of phenylmagnesium chloride. Man iso 3,3-bis (4-methoxyphenyl) -13- (2,5-dimethylphenyl) -13-hydroxy  indeno (2,1-f] naphtho [1,2-b] pyran (0.5 g) as a beige solid, which is obtained by means of NMR spectrum was identified.

Preparation of the specimens

500 ppm of the respective photochromic dye are used in the Monomer (TRANSHADE-150 from Tokuyama, refractive index 1.52) dissolved at room temperature with stirring. After addition of an initiator Alkylperoxyester type (1.5 wt .-%) is degassed twice and at closing after the temperature recommended by the company Tokuyama program polymerized. The glass molds are colored black, so the entirety of the photochromic dyes in the unexcited state can be incorporated into the matrix. After completion of the polymerization If the specimens are annealed for 2 h at 100 ° C.

Recording the kinetic curves

To determine the whitening speeds, the Pro Be measured in a conventional kinetikbank (irradiation with 50 klux according to EN 1836 point 6.1.3.1.1.). The exposure time is 15 minutes, the lightening takes place in the dark. During exposure and up The transmission is evaluated according to the light sensitivity of the human eye V λ - recorded. The temperature of the glass will be controlled by a thermostated cuvette.

Claims (1)

1. Photochromic pyrans with the general structural formula
characterized in that
R ₁ and R _{2 are} independently 1 to 2 (m, n = 0, 1, 2) are substituents from the group F, which consists of C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, chloro or fluoro or from a group consisting of C ₅ -C ₆ ) cycloalkyl, phenyl, benzyl, dialkyl (C ₁ -C ₆ ) amino, dicyclohexylamino, diphenylamino, piperidyl, morpholinyl or pyridyl.
Or two R ₁ and / or two R ₂ independently form together a carbo- or heterocyclic ring from the group of benzo, pyrido, pyrazino, pyrimidino, furano and thiopheno.
R _{4 is} a substituent from the group G,
consisting of hydrogen, hydroxy, C ₁ -C ₆ alkyl, C ₅ -C ₆ cycloalkyl, C ₁ -C ₆ acyl, C ₁ -C ₆ alkoxy, phenyl, benzyl, monosubstituted phenyl, monosubstituted benzyl, chloro and fluoro, wherein the aryl substituents are C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy;
or monochloro- or monofluoro- substituted phenyl, unsubstituted or monosubstituted naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, or indolyl, wherein the heterocycles are linked via the carbocycle to the naphthopyran system and the substituents the group chloro, fluoro, C ₁ -C ₆ al kyl or C ₁ -C ₆ alkoxy come;
or di- or trisubstituted phenyl, where the substituents from the group chloro, fluoro, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ ω-phenylalkyl or C ₁ -C ₆ ω-phenoxyalkyl removed become. The ω-ended phenyl ring can in turn represent the X, X 'or R ₄ radical of another photochromic pyrans system.
X and X 'either belong to the group Z, ie independently voneinan from

• a) the unsubstituted, mono-, di- and trisubstituted aryl groups phenyl and naphthyl,
• b) the unsubstituted, mono-, di- and trisubstituted heterocyclic groups pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl and benzothien-3-yl, wherein the substituents in a) and b) a group consisting of hydroxy, amino, mono (C ₁ -C ₆ ) alkylamino, di (C ₁ -C ₆ ) alkylamino, piperidino, morpholino, pyrryl, (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) chloroalkyl, (C ₁ -C ₆ ) fluoroalkyl, (C ₁ -C ₆ ) alkoxy, mono (C ₁ -C ₆ ) alkoxy (C ₁ -C ₄ ) alkyl, chloro and fluoro, were taken
• c) (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) chloroalkyl, (C ₁ -C ₆ ) fluoroalkyl, mono (C ₁ -C ₆ ) alkoxy (C ₁ -C ₄ ) alkyl, (C ₃ -C ₆₎ cycloalkyl, mono (C ₁ -C ₆₎ alkoxy (C ₃ - C ₆₎ cycloalkyl, chloro (C ₃ -C ₆₎ cycloalkyl and fluoro (C ₃ -C ₆₎ cycloalkyl selected or
  both together with the carbon atom of the point of attachment to the pyran form a saturated C ₅ -C ₁₀ monocyclic, C ₇ -C ₁₂ bicyclic or C ₇ -C ₁₂ tricyclic hydrocarbon ring or fluoro-9-ylidene;
  or either X or X 'is mono- or disubstituted phenyl substituted in position p for linking to - phenyl, - (CH ₂ ) _p -phenyl or -O- (CH ₂ ) _p - O -phenyl (p = 1, 2, 3, ..., 6), wherein the second phenyl ring belongs to a second - not necessarily identical - photaryromanic diarylpyrane;
  Y was taken from the group consisting of hydrogen, (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) acyl, unsubstituted benzoyl, unsubstituted naphthoyl, mono-substituted benzoyl and monosubstituted naphthoyl, where the said aryl substituents C ₁ - C _{6 are} alkyl or C ₁ -C ₆ alkoxy;
  with the proviso that R ₁ and R ₂ did not belong to group F when R _{4 was} taken from group G and X and X 'belonged to group Z.