DE19902771A1 - Photochromic spiro-fluoreno-pyran compounds, useful in plastic optical components, e.g. lenses, spectacle glasses, windows, blinds, covers, roofing etc. - Google Patents

Abstract

Photochromic spirofluorenopyran compounds. Photochromic spirofluorenopyrans of formula (I), in which: R1 = 1-6C alkyl or alkoxy, phenyl, bromine, chlorine or fluorine (group A); R2, R3, R4 = H or a group A substituent (group A'), or R1 + R2 and/or R3 + R4 = a benzo or pyrido ring (each optionally substituted with 1 or 2 group A substituents); G = a 5- to 8-membered ring (including the spiro carbon) onto which at least one ring system (group E) is condensed, such systems comprising benzene, naphthalene, phenanthrene, pyridine, quinoline, furan, thiophen, pyrrole, benzofuran, benzothiophen, indole and/or carbazole (all optionally mono- or di-substituted with group(s) A); B, B' = (a) phenyl or naphthyl (each with 0, 1, 2 or 3 Group F substituents), (b) pyridyl, furyl, benzofuranyl, thienyl, benzthienyl or julolidinyl (all with 0, 1 or 2 Group F substituents) or (c) groups of formula (c1) or (c2), or (d) B + B' may form a fluoren-9-ylidene system (with 0, 1 or 2 Group A substituents) or a saturated hydrocarbon system which is 3-12C spiro-monocyclic, 7-12C spiro-bicyclic or 7-12C spiro-tricyclic; F = OH, amino, mono- or di-(1-6C alkyl)-amino, mono- or di-phenyl-amino (with 0, 1 or 2 ring-substituents), piperidinyl, N-substituted piperazinyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, indolinyl, morpholinyl, carbazolyl, pyrryl (with 0, 1 or 2 substituents), 1-6C alkyl or alkoxy, Br, Cl or F, in which the substituents on the (hetero)aromatic groups may be 1-6C alkyl or alkoxy, Br, Cl and/or F; Y, Z = O, S, CH, CH2 or NRN; RN = 1-6C alkyl or acyl, phenyl or H; R<5> = OH or a Group A substituent; m = 0, 1 or 2; R6, R7 = H and/or 1-6C alkyl

Description

The invention relates to photochromic spirofluorenopyrans and their use. It han the compounds of the invention are photochromic pyran compounds, derived from 9H-fluorene, with the carbon atom in the 9-position wide ren ring system and thus forms a spiro junction.

Various classes of dyes have been known for a long time, which be when irradiated with light tuned wavelengths, especially sun rays, reversibly change color. This is due to the fact that these dye molecules are excited by light energy Change state, which they leave when the power supply is interrupted and in return to their original state. These photochromic dyes include different pyran systems in the prior art with different basic systems and substituents have already been described.

State of the art

Pyranes, especially naphthopyrans and larger ring systems derived from them, are currently the most processed class of photochromic compounds. Although already in The first patent application in 1966 (US 3,567,605) was only made in the 1990s Connections are being developed that appeared suitable for use in spectacle lenses. A suitable class of compounds of pyrans are, for example, 2,2-diaryl-2H-naph tho [1,2-b] pyrans or the 3,3-diaryl-3H-naphtho [2,1-b] pyrans, which in excited form show different colors, such as yellow, orange or red-orange. As another verb The class of photochromic compounds are the indeno-fused naphthopyrans from Interest that absorb longer waves due to their larger ring system. these can  either from the 2H-naphtho [1,2-b] pyrans or the 3H-naphtho [2,1-b] pyrans guided systems, being characterized by annealing on the f-side of the naphthalene part the respective naphthopyran systems emerge.

Several publications deal with indeno-fused naphthopyrans derived from the 2H-naphtho [1,2-b] pyrans:
WO 97/48762, WO 97/48993 and US 5,723,072 describe naphthopyran compounds with a substituted or unsubstituted indeno group, the 2,1 positions of which have the f-side of the naphthalene part of a 2H-naphtho [1,2-b ] pyrans are fused, the pyran ring having special substituents. In WO 97/48993 and US 5,723,072 an un-, mono- or disubstituted heterocyclic ring on the g-, h-, i-, n-, o- or p-side of the indenonaphthopyran can also be fused to this basic system be. Accordingly, the Indeno [2,1-f] naphtho [1,2-b] pyrans with a very wide range of possible substituents are disclosed, although in these publications there is no ring formation between the substituents R ₁ and R ₂ on the carbon atom no. 13 is described under formation of a spiro carbon atom. A spiro compound is only ever disclosed directly on the pyran ring at the substituents B and B '; In contrast, other spiro compounds are claimed according to the invention.

WO 96/14596, PCT / DE 98/02820, US 5,645,767, WO 98/32037 and US 5,698,141 describe photochromes derived from 2H-naphtho [1,2-b] pyran indeno-fused naphthopyran dyes, the compositions containing them as well a process for their manufacture. In US 5,698,141 can additionally on this Basic system an un-, mono- or disubstituted heterocyclic ring on the g-, h-, i-, n-, o- or p-side of the indenonaphthopyran must be fused. From the very extensive Chen list of substituents also includes very special spiro compounds, namely sol systems with a spiroheterocyclic group, including the spiro atom at the 13-position of the basic system there is a 5- to 8-membered ring that always contains 2 oxygen atoms contains, is present.  

However, the various known photochromic dyes have disadvantages bound, the comfort of the glasses when used in sun protection glasses significantly affect the wearer. The known dyes are not sufficient long-wave absorption in the excited as well as in the non-excited state. There is one too high temperature sensitivity of the darkening before, at the same time often too slow brightening occurs. In addition, the dyes described often have one insufficient lifespan and thus allow only a short shelf life of the sun protective glasses. The latter results in rapidly declining performance and / or strong ver yellowing noticeable.

In the prior art, the expert also finds hardly any information about where and with which substituents a pyran is to be substituted in order to obtain a specific long-wave To reach absorption maximum.

In cases where certain substitution patterns set an absorption maximum, this also defines the kinetic properties, such as darkening and brightening speed, temperature dependence u. a. Any influence on the kinetics in both directions, faster or slower, and practically without influence on the absorption maximum, was previously not possible.

Background of the Invention

The present invention is therefore based on the object of a new class photo provide chromic compound that has significantly improved properties over the have structures described in the prior art. In addition, it is intended for the subject be made possible by appropriate selection rules for the respective use tailor-made properties such as absorption maximum (color), brightening speed u. a. to achieve.

The above-mentioned object of the invention is achieved by the photochromic Spirofluore nopyrane of the formula (I):

wherein
R _{1 is} a substituent selected from group A consisting of (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) alkoxy, phenyl, bromine, chlorine and fluorine;
R ₂ , R ₃ and R _{4 are} independently the same or different and represent a substituent selected from the group A 'consisting of hydrogen and the substituents of group A; or
(R ₁ together with R ₂ ) and / or (R ₃ together with R ₄ ) independently of one another represent an unsubstituted, mono- or disubstituted benzo or pyrido ring, the substituents of which are selected from group A;
G, including the spiro carbon atom, represents a 5- to 8-membered ring to which at least one aromatic or heteroaromatic ring system is fused, the ring system or rings being selected from group E, consisting of benzene, naphthalene, phenanthrene, pyridine , Quinoline, furan, thiophene, pyrrole, benzofuran, benzothiophene, indole and carbazole, which in turn can have one or two substituents selected from group A; and
B and B 'are independently selected from the following groups a), b), c) or d), with

• a) phenyl or naphthyl which are unsubstituted, mono-, di- and tri-substituted; or
• b) the heterocycles pyridyl, furanyl, benzofuranyl, thienyl, benzothienyl and julolidinyl, which are unsubstituted, mono- or disubstituted;
  wherein the substituent (s) of the aryl or heteroaryl groups in a) and b) from a group F consisting of hydroxy, amino, mono- (C ₁ -C ₆ ) alkyl amino, di- (C ₁ -C ₆ ) - alkylamino, on the phenyl ring unsubstituted, mono- or disubstituted mono- and diphenylamino, piperidinyl, N-substituted piperazinyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, indolinyl, morpholinyl, carbazolyl, un-, mono- and disubstituted pyrryl, (C ₁ -C ₆ ) -alkyl, (C ₁ -C ₆ ) -alkoxy, bromine, chlorine and fluorine are selected, the substituent (s) on the aromatics and heteroaromatics being selected from a group consisting of (C ₁ -C ₆ ) -alkyl, ( C ₁ -C ₆ ) alkoxy, bromine, chlorine and fluorine are selected; or
• c) the groups with the following structure diagrams:
  wherein
  Y and Z independently of one another from the group O, S, CH, CH ₂ , NR ^N and the nitrogen substituents R ^N from the group consisting of (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) acyl, Phenyl and hydrogen, are selected and
  the substituents R _{5 are selected} from the group A and hydroxy, where
  m = 0, 1 or 2, and
  R ₆ and R _{7 are} independently hydrogen and / or (C ₁ -C ₆ ) alkyl; or
• d) B and B 'together represent un-, mono- or disubstituted fluoren-9-ylidene or a saturated hydrocarbon which is C ₃ -C ₁₂ -spiro-monocyclic, C ₁ -C ₁₂ -spiro-bicyclic and / or C. ₇ -C ₁₂ -spiro-tricyclic, the fluorene substituents being selected from group A.

Accordingly, the ring system G, with the addition of the spiro carbon atom, forms a 5- membered to 8-membered ring. At least one aromatic or heteroaromatic ring system annellated. That or the fused ring systems can According to the invention can be selected independently of one another from the group consisting of Benzene, naphthalene, phenanthrene, pyridine, quinoline, furan, thiophene, pyrrole, benzofuran, Benzothiophene, indole and carbazole. Of course, the ring systems can both as well as mono- or disubstituted, the substituent (s) from the above defi nated group A are selected.

In the present invention, C ₃ -C ₁₂ -spiro-monocyclic is to be understood as a 3-membered to 12-membered ring known to the person skilled in the art. C ₁ -C ₁₂ -spiro-bicyclic systems which may be present according to the invention also belong to the knowledge of the person skilled in the art. Examples include norbornane, norbornene, 2,5-norbornadiene, norcaran and pinan. A known spiro-tricyclic system that can be used in the invention is, for example, adamantane.

The invention also relates to photochromic spirofluorenopyrans of the formula (II):

wherein R ₁ to R ₄ , B and B 'are as defined above;
X is either a single bond or is selected from the group consisting of

-O-, -S-, (CR ₂ ) _n - with n = 1, 2 or 3,
-D = D'- with D, D '= N, CR or
-L-L'- with L, L '= O, S, NR, CHR or CR ₂ ,

where R = H, (C ₁ -C ₆ ) alkyl or phenyl and L and L cannot both be O or S at the same time; and
C and C 'are independently selected from group E defined above, each of which may have one or two substituents selected from group A.

When X is referred to as "single bond" in the present specification is, this means that between the ring systems C and C 'there is an immediate link, d. H. no atom other than Bridging should serve.

According to a further preferred embodiment of the invention, X represents a single bond, the two ring systems C and C 'present being bridged by a further link in the ortho, ortho' position to the first link. Such a bridging encompasses any possibility known to the person skilled in the art to connect the two ring systems C and C ', for example by means of heteroatoms such as oxygen or sulfur, saturated or unsaturated C ₂ to C ₅ carbon chains or the like. For example, the further linkage in the ortho, ortho 'position can lead to a 4,5-phenanthryl spiro compound, the spiro compounds according to the invention then having the following general structure (III):

It can also be advantageous if in the spiro compounds B and B 'are selected independently of one another from group a) or d). Especially before adds B and B 'independently of one another unsubstituted or monosubstituted phenyl or Naphthyl, wherein the substituent in each case selected from the group F defined above is. In the photochromic spiro compounds according to the invention, B and B 'can also be the same substituents.

According to a further preferred embodiment of the invention, C and C 'are independent gig unsubstituted or monosubstituted phenyl or naphthyl, the substituent is selected from group A. C and C 'can also have the same substituents represent.

The following photochromic spirofluorenopyrans according to the invention have particularly advantageous properties:

• 1) Spiro-9-fluorene-13 '- [3,3-diphenyl-6-methoxy-indeno [2,1-f] naphtho [1,2-b] pyran];
• 2) Spiro-9-fluorene-13 '- [6-methoxy-3- (4-methoxyphenyl) -3-phenyl-indeno [2,1-f] -naph tho [1,2-b] pyran];
• 3) Spiro-9-xanthene-13 '- [6-methoxy-3- (4-methoxyphenyl) -3-phenyl-indeno [2,1-f] -naph tho [1,2-b] pyran];
• 4) Spiro-9-fluorene-13 '- [3,3-bis (4-methoxyphenyl) -6-methoxy-indeno [2,1-f] naphtho [1,2-b] pyran];  
• 5) Spiro-9-xanthene-13 '- [3,3-bis (4-methoxyphenyl) -6-methoxy-indeno [2,1-f] -naph tho [1,2-b] pyran];
• 6) Spiro-9- (9,10-dihydroanthracene) -13 '- [3,3-bis (4-methoxyphenyl) -6-methoxy-inde no [2,1-f] naphtho [1,2-b] pyran];
• 7) Spiro-9-fluorene-13 '- {6-methoxy-3- [4- (N-morpholinyl) phenyl] -3-phenyl-indeno [2,1- f] -naphtho [1,2-b] pyran};
• 8) Spiro-9-fluorene-13 '- [3- (4-dimethylaminophenyl) -6-methoxy-3-phenyl-indeno [2.1-1] naphtho [1,2-b] pyran];
• 9) Spiro-9-fluorene-13 '- [3- (4-diphenylaminophenyl) -6-methoxy-3-phenyl-indeno [2,1-f] naphtho [1,2-b] pyran];
• 10) Spiro-9-fluorene-13 '- [3,3-bis (4-methoxyphenyl) -indeno [2,1-f] naphtho [1,2-b] pyran];
• 11) Spiro-9-fluorene-13 '- {3- [4- (N-morpholinyl) phenyl] -3-phenyl-indeno [2,1-f] naphtho- [1,2-b] pyran};
• 12) Spiro-9-fluoren-11 '- [3,3-bis (4-methoxyphenyl) -5-bromofluoreno [2,1-b] pyran] or
• 13) Spiro-9-fluoren-13 '- [3,3-bis (4-methoxyphenyl) -5-bromo-benzo [1] fluoreno [2,1 -b] py ran].

The invention further relates to the use of one or more of the photochromic Spirofluorenopyrans in plastics of all kinds, especially for ophthalmic purposes. For example, the photochromic dyes according to the invention in lenses, glasses for glasses of all kinds, such as ski goggles, sunglasses, motorcycle glasses, visors of protective helmets, and the like can be used. In particular, the fiction According to spirofluorenopyrans also for sun protection purposes in vehicles, apartments in Form of windows, protective covers, covers, roofs or the like Find.

The compounds according to the invention are distinguished by a large number of advantages:
It is a completely new class of photochromic compounds which do not have the disadvantages of the compounds known in the prior art. Surprisingly, the spiro compounds according to the invention, ie by linking the free substituents usually located on the central carbon atom of the fluorene structure to form a closed ring system, at least one aromatic and / or heteroaromatic system being present as an additional component of the new ring, the aforementioned problems of the connections from the prior art are overcome. The closest compounds described in the prior art are the indeno-fused naphtho pyrans disclosed in PCT / DE 98/02820. From these naphthopyrans, compounds in the form of so-called "carbinols" can be derived with the knowledge of the present invention. Both in relation to the closest known compounds and the derived compounds, the desired influence on the brightening and significant improvements in the service life were achieved in the spiro compounds according to the invention. Yellowing, as is observed with the carbinols, no longer occurs in the spiro compounds according to the invention. It is completely unexpected that, despite the electronic decoupling of the new structural parts according to the invention from the color center, a different, much clearer color impression occurs in the excited form.

All of these spiro compounds of the invention are therefore distinguished from that closest state of the art also characterized by better aging behavior, so probably in terms of performance as well as in terms of color retention. Since these closest ver bindings belong to the class of indeno-fused naphthopyrans these are particularly appreciated in the prior art.

The properties of the spiro compounds according to the invention should be based on some ver Bonds are explained, the invention of course not on this Ausfüh is limited.

Brightening rate and longest wave absorption maximum λ _max

The influence of the substituents R ' ₁ -R' ₃ on the brightening rate within 10 min (Δ _{10 min} = [(τ _{10 min} -τ _s ) / (τ ₀ -τ _s )]) and the longest-wave absorption maximum λ _{max was} Spiro compounds according to the invention (X = single bond) examined. The chemical structural formulas of the spiro and carbinol compounds used are shown as follows, where R ₁ 'is either hydrogen or selected from group A, R ₂ ' and R ₃ 'are independently selected from hydrogen or from group F and R ₄ 'is selected such that the corresponding spiro compound results from cyclization.

The results of the measurements are summarized in Table 1.  

Table 1

The compounds according to the invention are shown in Table 1 for the sake of clarity "Spiro" abbreviated, the subsequent number immediately referring to the corresponding one Example in which the preparation of this compound is described.

It can be seen from Table 1 that an electron-donating substituent on R ' ₁ (OCH ₃ instead of H) λ _max shifts bathochromically by 20-25 nm, the brightening rate remaining approximately the same. The same substitution at R ' ₂ leads to a bathochromic shift of only 10 nm, the brightening rate increases by almost 30%. With more electron-donating substituents, λ _max can be shifted bathochromically up to 50 nm. Another OCH ₃ group instead of H at R ' ₃ again results in a further bathochromic shift by 10 nm and an increase in the rate of lightening by more than 30%. As will be shown, the teaching according to the invention allows both the longest wavelength absorption maximum and the lightening rate to be tailored to the particular application in a very wide range by suitable choice of the substituents R ' ₁ -R' ₃ .

In the following, the influence of the spiro linkage on the brightening rate within 10 min (Δ _{10 min} = [(τ _{10 min} -τ _s ) / (τ ₀ -τ _s )]) and the longest-wave absorption maximum λ _{max was} examined. Carbinol compounds were compared with the corresponding spiro compound according to the invention and the data obtained were compared.

The results obtained are shown in Table 2.  

Table 2

The connections based on the prior art are shown in Table 2 of the overview for the sake of simplicity abbreviated to "carbinol", the subsequent number immediately to the corresponding example, in which the preparation of this compound is described, relates.

As can be seen from Table 2, the influence of the spiro linkage on the longest wave Absorption maxima very low. Compared to the identical carbinol starting compound There is only a hypsochromic shift of 5-10 nm. The brightening However, speed can be influenced as desired depending on the type of spiro link are: A direct link is accelerated, an oxygen bridge leaves unchanged and a methylene bridge slows down the brightening rate.

This is shown graphically in Fig. 1 for the Spiro connections Spiro 4-6. The Measurement took place at 23 ° C, 15 min. Exposure, at 50 klux and 10 min dark lightening. Here, the different transmission values became visible after 15 min exposure equidistant comparison.

It is now possible with the teaching according to the invention, after having used R ' ₁ -R' _{3 to} optimally adapt the other properties of the photochromic compound (including absorption behavior, migration behavior, affinity to the polymer matrix) to the respective application, by means of R ' ₄ adjust the kinetics, ie the brightening rate and thus the temperature dependence of the photochromic reaction, as desired. When selecting the color, only the slight hypsochromic shift due to the Spiro link must be taken into account when selecting R ' ₁ -R' ₃ .

This completely surprising effect of the different spiro link bridges is for the spiro compounds according to the invention are just as unpredictable as the ver better behavior in the life test.  

Yellowness index increase Δyi and performance maintenance LE in the life test

Furthermore, the yellow index increase Δyi and the power retention LE were determined in the life test (50 h xenon lamp). The following applies:

Δyi = yi _{after 50h xenon} test -yi _{before xenon test} ; LE = (τ _{s before xenon test} / τ _{s after 50h xenon test} )

The compounds used are based on their chemical structural formulas shown.

The results obtained are shown in Table 3.  

Table 3

Compared to the corresponding carbinol compounds, which are structurally the state of the art nik come close, is common in the spiro compounds of the invention better preservation of photochromic performance. In individual cases, as in Examples 4 and 6, The power loss after 50 h Xenon test is only 2% for the Spiro connections, however 20% for the carbinols. In long-term use in ophthalmic glasses, the Eyeglass wearers with the compounds of the invention with a multiple of Calculate wearing time.

The reduction in the yellow index is even more dramatic and also completely surprising Change in the fully darkened state after 50 h Xenon test, in all cases. This was not to be expected and is also not due to the absence of the hydroxyl group in the spiro Compound attributed, since some carbinols only a small (No. 3), others against show an extreme yellow index change (No. 6).

In Figs. 2, 3 and 4, the a * / b * -Farbortkurven three carbinol or spiro compounds before and after 50 hours of Xenon test are shown. The measurements were carried out at 23 ° C, 15 min. Exposure, at 50 Klux and 10 min. Dark lightening. Here it can be clearly seen that the color locus of the carbinols shifts dramatically over the course of a darkening and brightening cycle due to aging, while the corresponding spiro compounds remain true to color over the course of aging. This is impressively demonstrated by the position of the measurement curves of the carbinol or spiro compound before and after the xenon aging test.

Two conditions are of particular importance for the wearer of the glasses: the brightened and the fully darkened state. In contrast to the intermediate states, these become qua experienced stationary. All three exemplary bridge systems of the Spiro according to the invention bridging show practically no old age compared to the corresponding carbinols tendency. This is even more important for the use in glasses than the pure lei Conservation of performance, as experience has shown that the wearer of the glasses has a slight decrease in the on  Darkness performance not noticed during extended use. A slight color change on the other hand is quickly noticed and claimed as a defect.

The preparation of the spiro compounds of the invention is explained below using the general synthetic route. For this purpose, reference is made to the general synthesis scheme which is shown in FIGS. 5 and 6:
The substituted or unsubstituted benzo- or naphthophenones (a) used as starting material are either commercially available or can be obtained easily and mostly in good yields by Friedel-Crafts acylation in step (1). The radicals R ₃ and R ₄ correspond to the substituents already defined above. (R ₁ ') _m is selected from group A, where m = 0, 1 or 2.

In step (2), the half ester is obtained via a Stobbe condensation using succinic acid diester (b) generated. If the two rings connected via the keto group are not identical, a mixture of isomers is formed. Deviating from the representation in WO 96/14596, in of the present invention continued with the mixture of isomers. The separation of the honey-like, usually non-crystallizing isomers is very complex, it can on the synthesis route chosen according to the invention can be carried out very easily later. On finally the half ester mixture with aqueous alkali according to step (3) to the isomeric mixture of diacids (c) saponified. By heating with acetyl chloride in step (4) the isomer mixture of the cyclic anhydrides (d) manufactured.

In step (5) with aluminum chloride by intramolecular 5-ring cyclization Isomer mixture (s) synthesized. These compounds crystallize very well and can in most cases thanks to their different solubility in benzene easily in the two Isomers are separated. The desired isomer is formed under the influence of Acetic anhydride by intramolecular 6-ring cyclization according to step (6) of the esters (f). This is then saponified in step (7) alkaline to give the hydroxy-fluorenone derivative (g).

The reaction with a 2-propin-1-ol derivative (step (8)), in which B and B 'are as defined above, leads to the weakly photochromic, strongly dark red colored indeno-fused naphthopyrans (h). This reaction is not described in detail here, since it can be carried out in a manner analogous to that of 1- or 2-naphthols. Examples of this can be found, inter alia, in US 5,066,818, US 5,238,981 and EP 0 246 114. With appropriate Grignard compounds, the compounds (i) referred to as so-called carbinols in the present invention are formed in step (9), where R ' _{4 is selected} from such that the corresponding spiro compounds can be formed with the ring G defined above. The free hydroxyl group in (i) is then cyclized according to step (10) with acetic acid / hydrochloric acid to give the corresponding spiro compounds (k).

The aforementioned synthetic route now has various advantages over the route recommended in WO 96/14596 or US 5,645,767:
On the one hand, various connections cannot be represented in the way described in WO 96/14596 or US Pat. No. 5,645,767. The route described above is much gentler, for example, heating with concentrated phosphoric acid to over 190 ° C is no longer necessary. As a result, more sensitive groups can also be used as substituents. The closure of the 5-ring in front of the 6-ring in the above method likewise frequently leads to products which cannot be or are difficult to display on the way closure of the 6-ring in front of the 5-ring mentioned in the prior art. On the other hand, even with the same target product, e.g. B. with symmetrical benzophenones as starting material, fewer by-products according to the process described above, with easier cleaning and higher yields of the photochromic dye. The exact synthetic procedure is described in detail in the presentation of the following examples, these examples, of course, not restricting the scope of the present invention, but are only intended to be illustrative.

EXAMPLE 1

Steps i) to vi) of this example were carried out on the basis of the method described in J.Chem. Soc. 1958, P. 986ff by F.G. Baddar, L.S.El-Assal and V.B. Bagho's published article with some Modifications carried out.

i) tert. Butanol is melted beforehand in a warm water bath. Potassium tert. -butylate (30 g) is tert in a 1l three-necked flask in 600 ml. Suspended butanol and 4-methoxy benzophenone (50 g) and dimethyl succinate (45 g) were added. The mixture will stirred well and heated under reflux for 1 h. Then potassium tert-butoxide is added again (30 g) and dimethyl succinate (45 g) and allowed to reflux for 2 h. After cooling, hydrolyzed with a total of 2 l of water. With stirring conc. Acidified hydrochloric acid. It is then extracted twice with 400 ml of ether, and the combined ether phases are washed once with 400 ml of water. Then it will be extracted twice with 500 ml of saturated sodium bicarbonate solution. It works Product as carboxylate in the aqueous phase, which was washed once with 200 ml of ether and then in a large beaker while stirring with conc. Acidified hydrochloric acid becomes. The mixture is then extracted twice with 400 ml ether and the organic phase washed once with water. After drying over sodium sulfate, the ether becomes thorough rotated. The orange-yellow, honey-like reaction product (75 g) was analyzed by NMR Spectrum identified as 3-methoxycarbonyl-4- (4-methoxyphenyl) -4-phenyl-3-butenoic acid.

ii) 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 brown reaction solution formed is heated under reflux for 3 h. After cooling, stirring and good cooling in the ice bath with conc. Acidified hydrochloric acid. Then twice with 400 ml of vinegar ester extracted. The combined ethyl acetate phases are washed once with water and spun thoroughly after drying over sodium sulfate. The honey-like reak tion product (70 g) was determined by means of NMR spectrum as 3-carboxyl-4- (4-methoxyphenyl) -4- phenyl-3-butenoic acid identified.  

iii) The above reaction product is dissolved in 300 ml of acetic acid with acetyl chloride (35 g). The mixture is then heated under reflux with stirring for 2 h. After distilling off the solvent the residue while still warm was dissolved in about 600 ml of ethyl acetate and twice with water extracted. Then is twice with 300 ml of 5% sodium carbonate solution extracted. The organic phase is washed again with water, over sodium sulfate dried and spun thoroughly. The reaction product (60 g) falls as a dark, viscous Oil on and was bern as NMR (4-methoxyphenyl-phenyl-methylene) succinic anhydride identified.

iv) The above reaction product is in about 600 ml of dichloromethane at room temperature dissolved and then cooled well in an ice bath. Then with good stirring and Cool aluminum chloride (35 g) was added in portions and the mixture was left over Thaw at night. The reaction mixture is then hydrolysed in 1 l of ice / water poured. After separating the organic phase, this is twice with 500 ml of water washed and then extracted twice with 600 ml of 5% sodium hydroxide solution. After Washing the combined aqueous alkaline phases with 250 ml of ether is concentrated. Acidified hydrochloric acid with stirring. It is extracted twice with 400 ml of ethyl acetate and the organic phase washed with water, dried over sodium sulfate and thoroughly rotated. A brown solid residue (45 g) remains, which according to the NMR spectrum the mixture of isomers 3- (4-methoxy-phenyl) -indenone-2-acetic acid and 6-methoxy-3- phenyl-indenone-2-acetic acid. The isomers are separated by hot digestion in benzene. After cooling and suction filtration of the suspension, pure residue is obtained 3- (4-methoxyphenyl) -indenone-2-acetic acid as orange-yellow crystals (25 g).

v) The above reaction product is suspended in about 300 ml of acetic anhydride. After Adding sodium acetate (20 g) the mixture is stirred and refluxed for 3 hours heated. The product turns out thick when it cools down. After cooling to room temperature (and briefly in the fridge) the soft, crystalline, orange-brown one that forms The precipitate is filtered off and washed with a little acetic anhydride until the filtrate is no longer expires dark brown. Then it is washed thoroughly with water and at 60 ° C dried. The product (bright orange solid; 25 g) was treated with NMR spectrum identified as 5-acetoxy-3-methoxy-7H-benzo [c] fluoren-7-one.  

vi) The above reaction product is suspended in 400 ml of ethanol and with potassium hydroxide (25 g) was added. The reaction mixture becomes reflux with stirring for 1.5 hours heated, whereby a magnificent deep blue color can gradually be observed. After Cooling, about half of the ethanol is spun off and the remaining residue heated together with 1 liter of water on the hotplate until a deep blue solution is formed Has. Then the solution is removed from the hotplate and still hot with stirring conc. Acidified hydrochloric acid. A dark purple suspension is formed, which is stirred is cooled to room temperature. The suspension is suctioned off and carefully Washed water. The soaked material is still very muddy and becomes as good as possible sucked dry on the diaphragm pump. After drying at 60 ° C red-violet product (20 g) by means of NMR spectrum as 5-hydroxy-3-methoxy-7H-ben zo [c] fluoren-7-one identified.

vii) 3 g of the above reaction product are combined with 1,1-diphenyl-1-propinol (4 g; prepared from benzophenone and sodium acetylide in DMSO) in about 300 ml of toluene sus oscillates. After adding a spatula tip of 4-toluenesulfonic acid, the reaction mixture Heated under reflux for 1.5 h. In the course of the reaction, the poorly soluble initially works Naphthol educt more and more in solution; a red reaction solution is formed. After briefly cooling, the toluene is spun off in vacuo and the residue in 40 ml of Di Chloromethane dissolved and a column chromatography with aluminum oxide (water content 3%) as a stationary and dichloromethane / hexane mixture (2: 1) as a mobile phase For final cleaning, the product is digested in about 100 ml of methanol and slightly warmed. After cooling, the resulting suspension is suctioned off with methanol washed and dried. The dark red product (3 g) was determined by means of NMR spectrum 3,3-Diphenyl-6-methoxy-13-oxo-indeno [2,1-f] naphtho [1,2-b] pyran was identified.

viii) 2 g of the above reaction product is dissolved in 50 ml of absolute THF with stirring. To this solution, 2 equivalents of 2-biphenylyl magnesium bromide (made from 2- Brombiphenyl and magnesium shavings in THF solution) and added the whole Room temperature stirred for 1 h. Then poured into water, acidified with conc. hydrochloric acid until the phases are clear and the organic phase separates. After extraction  with water, drying over sodium sulfate and spinning off the solvent remains dark brown oil, which crystallizes by adding methanol. Crystallizes the product not, it is stirred in an ice bath until crystals precipitate. The suspension is stirred a few more minutes at room temperature, then sucks off the precipitate and washes with it Methanol after. The resulting beige solid (1 g) was determined by means of an NMR spectrum as 13- (2-biphenylyl) -3,3-diphenyl-13-hydroxy-6-methoxy-indeno [2,1-f] naphtho [1,2-b] pyran identified (carbinol 1).

ix) 1 g of the above reaction product according to R.G. Clarkson, M. Gomberg, J. Am. Chem. Soc. 1930, p. 2881ff in 30 ml of glacial acetic acid cyclized in the heat. After encore a drop of hydrochloric acid is heated to boiling for a further 5 min and water is still hot added until the reaction solution becomes cloudy. After cooling, the failed one Aspirated precipitate, washed with water and carefully dried. To the final Purification, the solid is dissolved in 40 ml dichloromethane and a column chromatography topography with aluminum oxide (water content 3%) as stationary and dichloromethane / hexane Mixture (2: 1) subjected to the mobile phase. After digesting with methanol, it becomes pure slightly beige product (0.5 g) obtained, which by NMR spectrum as Spiro-9- fluoren-13 '- [3,3-diphenyl-6-methoxy-indeno [2,1-f] naphtho [1,2-b] pyran] was identified (Spiro 1).

EXAMPLE 2

The procedure is analogous to example 1, only in step vii) is the reaction carried out with 1- (4-methoxyphenyl) -1-phenyl-1-propinol (made from 4-methoxybenzophenone and Na triumacetylide in DMSO) instead of 1,1-diphenyl-1-propinol. 6-methoxy-3- (4-meth oxyphenyl) -3-phenyl-13-oxo-indeno [2,1-f] naphtho [1,2-b] pyran. This becomes analogous to Bei game 1 step viii) with 2-biphenylyl-magnesium bromide according to the NMR spectrum to 13- (2-Bi phenylyl) -13-hydroxy-6-methoxy-3- (4-methoxyphenyl) -3-phenyl-indeno [2,1-f] naphtho [1,2- b] pyran reacted (carbinol 2). This is cyclized to Spi analogously to Example 1 step ix) ro-9-fluoren-13 '- [6-methoxy-3- (4-methoxyphenyl) -3-phenyl-indeno [2,1-f] naphtho [1,2-b] py ran] (Spiro 2; 0.7 g), which was identified by means of the NMR spectrum.  

EXAMPLE 3

The procedure is analogous to Example 2, only in step viii) is the reaction carried out with 2-phenoxyphenyl magnesium bromide (made from 2-bromodiphenyl ether and magnesium in THF solution) instead of 2-biphenylyl magnesium bromide. According to the NMR spectrum 13- Hydroxy-6-methoxy-3- (4-methoxyphenyl) -13- (2-phenoxyphenyl) -3-phenyl-indeno [2,1-f] naphtho [1,2-b] pyran (carbinol 3). This is cyclized analogously to Example 1 step ix) Spiro-9-xanthene-13 '- [6-methoxy-3- (4-methoxyphenyl) -3-phenyl-indeno [2,1-f] naphtho [1,2- b] pyran] (Spiro 3; 0.4 g), which was identified by means of the NMR spectrum.

EXAMPLE 4

The procedure is analogous to example 1, only in step vii) is the reaction carried out with 1,1-bis (4-methoxyphenyl) -1-propinol (made from 4,4'-dimethoxybenzophenone and Na triumacetylide in DMSO) instead of 1,1-diphenyl-1-propinol. 3,3-bis (4-methoxy phenyl) -6-methoxy-13-oxo-indeno [2,1-f] naphtho [1,2-b] pyran. This becomes analogous to Bei game 1 step viii) with 2-biphenylyl-magnesium bromide according to the NMR spectrum to 13- (2-Bi phenylyl) -3,3-bis (4-methoxyphenyl) -13-hydroxy-6-methoxy-indeno [2,1-f] naphtho [1,2-b] py ran implemented (carbinol 4). This is cyclized analogously to Example 1 step ix) to give Spiro-9- fluorene-13 '- [3,3-bis (4-methoxyphenyl) -6-methoxy-indeno [2,1-f] naphtho [1,2-b] pyran] (spiro 4, 0.6 g), which was identified by means of the NMR spectrum.

EXAMPLE 5

The procedure is analogous to example 4, only in step viii) is the reaction carried out with 2-phenoxyphenyl magnesium bromide instead of 2-biphenylyl magnesium bromide. It comes out loud NMR spectrum 3,3-bis (4-methoxyphenyl) -13-hydroxy-6-methoxy-13- (2-phenoxy-phenyl) - indeno [2,1-f] naphtho [1,2-b] pyran (carbinol 5). This is analogous to example 1 step ix) cyclizes to spiro-9-xanthene-13 '- [3,3-bis (4-methoxyphenyl) -6-methoxy-indeno [2,1-f] naph tho [1,2-b] pyran] (Spiro 5; 0.9 g), which was identified by means of the NMR spectrum.  

EXAMPLE 6

The procedure is analogous to example 4, only in step viii) is the reaction carried out with 2-Benzylphenyl-magnesium bromide (made from 2-bromodiphenylmethane and magnesium in THF solution) instead of 2-biphenylyl magnesium bromide. According to the NMR spectrum 13- (2-benzylphenyl) 3,3-bis (4-methoxyphenyl) -13-hydroxy-6-methoxy-indeno [2,1-f] naphtho- [1,2-b] pyran (carbinol 6). This is cyclized analogously to Example 1 step ix) to give Spiro-9- (9,10-dihydroanthracene) -13 '- [3,3-bis (4-methoxyphenyl) -6-methoxy-indeno [2,1-f] naphtho- [1,2-b] pyran] (Spiro 6; 0.5 g), which was identified by means of the NMR spectrum.

EXAMPLE 7

The procedure is analogous to example 1, only in step vii) is the reaction carried out with 1- [4- (N-Morpholinyl) phenyl] -1-phenyl-1-propinol [made from 4- (N-morpholinyl) benzene zophenon (H. Kotsuki, Synthesis 1990, p. 1145) and sodium acetylide in DMSO] instead of 1.1- Diphenyl-1-propinol. 6-Methoxy-3- [4- (N-morpholinyl) phenyl] -3-phenyl-13-oxo is formed indeno [2,1-f] naphtho [1,2-b] pyran. This is analogous to example 1 step viii) with 2- Biphenylyl magnesium bromide according to the NMR spectrum to 13- (2-biphenylyl) -13-hydroxy-6- methoxy-3- [4- (N-morpholinyl) phenyl] -3-phenyl-indeno [2,1-f] naphtho [1,2-b] pyran (Carbinol 7). This is cyclized analogously to Example 1 step ix) to give spiro-9-fluorene-13 '- {6- methoxy-3- [4- (N-morpholinyl) phenyl] -3-phenyl-indeno [2,1-f] naphtho [1,2-b] pyran} (Spiro 7; 0.4 g), which was identified by means of the NMR spectrum.

EXAMPLE 8

The procedure is analogous to example 1, only in step vii) is the reaction carried out with 1- (4-Dimethylaminophenyl) -1-phenyl-1-propinol (made from 4-dimethylamino-benzo phenon and sodium acetylide in DMSO) instead of 1,1-diphenyl-1-propinol. The result is 3- (4- Dimethylaminophenyl) -6-methoxy-3-phenyl-13-oxo-indeno [2,1-f] naphtho [1,2-b] pyran.  

This is done analogously to Example 1 step viii) with 2-biphenylyl magnesium bromide NMR spectrum for 13- (2-biphenylyl) -3- (4-dimethylaminophenyl) -13-hydroxy-6-methoxy-3- phenyl-indeno [2,1-f] naphtho [1,2-b] pyran implemented. This becomes analogous to example 1 step ix) cyclizes to spiro-9-fluorene-13 '- [3- (4-dimethylaminophenyl) -6-methoxy-3-phenyl-inde no [2,1-f] naphtho [1,2-b] pyran] (Spiro 8; 0.6 g), which is identified by means of the NMR spectrum has been.

EXAMPLE 9

The procedure is analogous to example 1, only in step vii) is the reaction carried out with 1- (4-Diphenylaminophenyl) -1-phenyl-1-propinol [made from 4-Diphenylamino-benzo phenon (B. Staskun, J. Org. Chem. 1968, p. 3031) and sodium acetylide in DMSO] instead of 1.1- Diphenyl-1-propinol. 3- (4-Diphenylaminophenyl) -6-methoxy-3-phenyl-13-oxo is formed indeno [2,1-f] naphtho [1,2-b] pyran. This is analogous to example 1 step viii) with 2- Biphenylyl magnesium bromide according to the NMR spectrum to 13- (2-biphenylyl) -3- (4-diphenyl aminophenyl) -13-hydroxy-6-methoxy-3-phenyl-indeno [2,1-f] naphtho [1,2-b] pyran. This is cyclized analogously to Example 1 step ix) to give spiro-9-fluorene-13 '- [3- (4-diphe nylaminophenyl) -6-methoxy-3-phenyl-indeno [2,1-f] naphtho [1,2-b] pyran] (Spiro 9; 0.5 g), which was identified by means of the NMR spectrum.

EXAMPLE 10

The procedure is analogous to Example 4, only in step i) is the implementation carried out Benzophenone instead of 4-methoxybenzophenone. After step vii) 3,3-bis (4- methoxyphenyl) -13-oxo-indeno [2,1-f] naphtho [1,2-b] pyran. This becomes analogous to example 1 Step viii) with 2-biphenylyl-magnesium bromide according to the NMR spectrum to give 3,3-bis (4- methoxyphenyl) -13- (2-biphenylyl) -13-hydroxy-indeno [2,1-f] naphtho [1,2-b] pyran. This is cyclized analogously to Example 1 step ix) to give spiro-9-fluorene-13 '- [3,3-bis (4- methoxyphenyl) -indeno [2,1-f] naphtlio [1,2-b] pyran] (Spiro 10; 0.7 g), which by means of NMR spectrum was identified.  

EXAMPLE 11

The procedure is analogous to example 10, only in step vii) is the reaction carried out with 1- [4- (N-Morpholinyl) phenyl] -1-phenyl-1-propinol instead of 1,1-bis (4-methoxyphenyl) -1-propi nol. 3- [4- (N-Morpholinyl) phenyl] -3-phenyl-13-oxo-indeno [2,1-f] naphtho [1,2- b] pyran. This is analogous to Example 1 step viii) with 2-biphenylyl magnesium bromide according to the NMR spectrum to 13- (2-biphenylyl) -13-hydroxy-3- [4- (N-morpholinyl) phenyl] -3-phe nyl-indeno [2,1-f] naphtho [1,2-b] pyran implemented. This is analogous to example 1 step ix) cyclizes to spiro-9-fluorene-13 '- {3- [4- (N-morpholinyl) phenyl] -3-phenyl-indeno [2,1-f] naph tho [1,2-b] pyran} (Spiro 11; 0.6 g), which was identified by means of the NMR spectrum.

EXAMPLE 12

The procedure is analogous to Example 4, with the omission of steps i) to vi). As Starting material for step vii) is 3-bromo-2-hydroxyfluorenone (T.C. Thomas, J. Indian Chem. Soc. 1974, p. 814) was used instead of 5-hydroxy-3-methoxy-7H-benzo [c] fluoren-7-one. 3,3-bis (4-methoxyphenyl) -5-bromo-11-oxo-fluoreno [2,1-b] pyran is formed. This will analogous to Example 1 step viii) with 2-biphenylyl magnesium bromide according to the NMR spectrum to 11- (2-biphenylyl) -3,3-bis (4-methoxyphenyl) -5-bromo-11-hydroxy-fluoreno [2,1-b] pyran implemented. This is cyclized analogously to Example 1 step ix) to give spiro-9-fluorene-11 '- [3,3- bis (4-methoxyphenyl) -5-bromo-fluoreno [2,1-b] pyran] (Spiro 12; 0.4 g), which by means of NMR spectrum was identified.

Production of the test specimens

500 ppm of the respective photochromic dye are in the monomer used (TRANSHADE-150 from Tokuyama; refractive index 1.52) at room temperature Stirring dissolved. After the addition of an initiator of the alkyl peroxy ester type (1.5% by weight) degassed twice and then according to the one recommended by Tokuyama Polymerized temperature program. The glass molds are colored black so that the All of the photochromic dyes in the unexcited state in the matrix can be installed. After the polymerization, the test specimens are still Annealed at 100 ° C for 2 h.  

Determination of the kinetic values a * / b * color locations as well as long-wave absorption maxima

To determine the lightening speeds, the test specimens produced were in a Measure the PTM II kinetic bench from Zeiss (irradiation with 50 klux according to DIN EN 1836 point 6.1.3.1.1.). The exposure time is 15 min each, the brightening in Dark 10 min. The temperature of the glass is controlled by a thermostattable cell regulated. During exposure and brightening, the transmission is assessed according to the Sensitivity to light of the human eye V λ - in short time intervals recorded. In addition, the PTM II kinetic bench delivers in a short time intervals the a * / b * color location data of the test specimens according to CIE 1976 and at Exposure end of the UV / VIS spectrum of the darkened specimens, from which the long-wave absorption maxima can be determined.

Determination of the yellow index value yi and the performance maintenance LE

The yellowness index yi is determined in accordance with the ASTM D 1925-70 standard. To do this, the x / y / z color locus data of the test specimens determined according to CIE 1931 with the standard illuminant C. Each the greater the yellowness index value yi, the greater the yellowing. This value is particularly meaningful for life tests of the test specimens. To do this, the Test specimen 50 h in a SUNTEST CPS rapid exposure device from Heraeus (from permitted with a xenon lamp and a UV special glass filter with cutoff 290 nm) exposed. The difference between the yellow index values Δ yi before and after this xenon test is a measure of how much the specimen yellows in the life test. The performance maintenance LE is a measure of how deeply the specimen darkens after the life test, d. H. to what extent the photochromic dyes still react.

Claims (12)

1. Photochromic spirofluorenopyrans of the formula (I):
wherein
R _{1 is} a substituent selected from group A consisting of (C ₁ -C ₆ alkyl, (C ₁ -C ₆ ) alkoxy, phenyl, bromine, chlorine and fluorine;
R ₂ , R ₃ and R _{4 are} independently the same or different and represent a substituent selected from the group A 'consisting of hydrogen and the substituents of group A; or
(R ₁ together with R ₂ ) and / or (R ₃ together with R ₄ ) independently of one another represent an unsubstituted, mono- or disubstituted benzo or pyrido ring, the substituents of which are selected from group A;
G, including the spiro carbon atom, represents a 5- to 8-membered ring to which at least one aromatic or heteroaromatic ring system is fused, the ring system or rings being selected from group E, consisting of benzene, naphthalene, phenanthrene, pyridine , Quinoline, furan, thiophene, pyrrole, benzofuran, benzothiophene, indole and carbazole, which in turn can have one or two substituents selected from group A; and
B and B 'are independently selected from the following groups a), b), c) or d), with

• a) phenyl or naphthyl which are unsubstituted, mono-, di- or tri-substituted; or
• b) the heterocycles pyridyl, furanyl, benzofuranyl, thienyl, benzothienyl and julolidinyl, which are unsubstituted, mono- or disubstituted,
  wherein the substituent (s) of the aryl or heteroaryl groups in a) and b) from a group F consisting of hydroxy, amino, mono- (C ₁ -C ₆ ) alkyl amino, di- (C ₁ -C ₆ ) - alkylamino, on the phenyl ring unsubstituted, mono- or disubstituted mono- and diphenylamino, piperidinyl, N-substituted piperazinyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, indolinyl, morpholinyl, carbazolyl, un-, mono- and disubstituted pyrryl, (C ₁ -C ₆ ) -alkyl, (C ₁ -C ₆ ) -alkoxy, bromine, chlorine and fluorine are selected, the substituent (s) on the aromatics and heteroaromatics being selected from a group consisting of (C ₁ -C ₆ ) -alkyl, ( C ₁ -C ₆ ) alkoxy, bromine, chlorine and fluorine are selected; or
• c) the groups with the following structure diagrams:
  wherein
  Y and Z independently of one another from the group O, S, CH, CH ₂ , NR ^N and the nitrogen substituents R ^N from the group consisting of (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) acyl, Phenyl and hydrogen, are selected and
  the substituents R _{5 are selected} from the group A and hydroxy, where
  m = 0, 1 or 2, and
  R ₆ and R _{7 are} independently hydrogen and / or (C ₁ -C ₆ ) alkyl; or
• d) B and B 'together represent un-, mono- or disubstituted fluoren-9-ylidene or a saturated hydrocarbon which is C ₃ -C ₁₂ -spiro-monocyclic, C ₇ -C ₁₂ -spiro-bicyclic and / or C. ₇ -C ₁₂ -spiro-tricyclic, the fluorene substituents being selected from group A.

2. Photochromic spirofluorenopyrans, in particular according to claim 1, of the formula (II):
wherein R ₁ to R ₄ , B and B 'are as defined in claim 1;
X is either a single bond or is selected from the group consisting of
-O-, -S-, - (CR ₂ ) _n with n = 1, 2 or 3,
-D = D'- with D, D '= N, CR or
-L-L'- with L, L '= O, S, NR, CHR or CR ₂ ,
where R = H, (C ₁ -C ₆ ) alkyl or phenyl and L and L 'both cannot be O or S at the same time; and
C and C 'are independently selected from the group E defined in claim 1, each of which may have one or two substituents selected from group A. 3. Photochromic spirofluorenopyrans according to claim 2, characterized in that X represents a single bond and the two ring systems C and C 'by a white tere link in the ortho, ortho 'position to the first link are bridged. 4. Photochromic spirofluorenopyrans according to claim 3, characterized in that the further linkage in the ortho, ortho 'position with the two ring systems C and C goes to a 4,5-phenanthryl spiro compound. 5. Photochromic spirofluorenopyrans according to at least one of claims 1 to 4, characterized in that B and B 'independently of one another from group a) or d) are selected. 6. Photochromic spirofluorenopyrans according to claim 5, characterized in that B and B 'independently of one another unsubstituted or monosubstituted phenyl or naphthyl represent, wherein the substituent is selected from group F. 7. Photochromic spirofluorenopyrans according to at least one of the preceding An sayings, characterized in that B and B 'represent the same substituents len. 8. Photochromic spirofluorenopyrans according to at least one of the preceding An sayings, characterized in that C and C 'independently or represent monosubstituted phenyl or naphthyl, the substituent in each case is selected from group A.   9. Photochromic spirofluorenopyrans according to at least one of the preceding An sayings, characterized in that C and C 'represent the same substituents len. 10. Photochromic spirofluorenopyrans selected from the group consisting of:

• 1) Spiro-9-fluorene-13 '- [3,3-diphenyl-6-methoxy-indeno [2,1-f) naphtho [1,2-b] pyran];
• 2) Spiro-9-fluoren-13 '- [6-methoxy-3- (4-methoxyphenyI) -3-phenyl-indeno [2,1-f] naphtho [1,2-b] pyran];
• 3) Spiro-9-xanthene-13 '- [6-methoxy-3- (4-methoxyphenyl) -3-phenyl-indeno [2,1-f] - naphtho [1,2-b] pyran];
• 4) Spiro-9-fluorene-13 '- [3,3-bis (4-methoxyphenyl) -6-methoxy-indeno [2,1-f] naphtho- [1,2-b] pyran];
• 5) Spiro-9-xanthene-13 '- [3,3-bis (4-methoxyphenyl) -6-methoxy-indeno [2,1-f] naphtho [1,2-b] pyran];
• 6) Spiro-9- (9,10-dihydroanthracene) -13 '- [3,3-bis (4-methoxyphenyl) -6-methoxy indeno [2,1-f] naphtho [1,2-b] pyran] ;
• 7) Spiro-9-fluorene-13 '- {6-methoxy-3- [4- (N-morpholinyl) phenyl] -3-phenyl-inde no [2,1-f] -naphtho [1,2-b ] pyran};
• 8) Spiro-9-fluorene-13 '- [3- (4-dimethylaminophenyl) -6-methoxy-3-phenyl indeno [2,1-f] -naphtho [1,2-b] pyran];
• 9) Spiro-9-fluorene-13 '- [3- (4-diphenylaminophenyl) -6-methoxy-3-phenyl indeno [2,1-f] -naphtho [1,2-b] pyran];
• 10) Spiro-9-fluorene-13 '- [3,3-bis (4-methoxyphenyl) -indeno [2,1-f] naphtho [1,2-b] pyran];
• 11) Spiro-9-fluorene-13 '- (3- [4- (N-morpholinyl) phenyl] -3-phenyl-indeno [2,1- f] naphtho- [1,2-h] pyran];
• 12) Spiro-9-fluorene-11 '- [3,3-bis (4-methoxyphenyl) -5-bromo-fluoreno [2,1-b] pyran] or
• 13) Spiro-9-fluoren-13 '- [3,3-bis (4-methoxyphenyl) -5-bromo-benzo [1] fluoreno [2,1-b] pyran].

11. Use of one or more of the photochromic spirofluorenopyrans after min at least one of claims 1 to 10 in plastics of all kinds, in particular for ophthalmic purposes. 12. Use of one or more of the photochromic spirofluorenopyrans after at least one of claims 1 to 10 in plastic articles, in particular Lenses, glasses for glasses of all kinds, such as ski goggles, sunglasses, motorcycle glasses, Safety glasses, visors for protective helmets, windows, protective covers, covers, Roofs or the like.