EP1664034A1

EP1664034A1 - Substituted phenanthropyrans

Info

Publication number: EP1664034A1
Application number: EP04764351A
Authority: EP
Inventors: Claudia Mann; Manfred Melzig; Udo Weigand
Original assignee: Rodenstock GmbH
Current assignee: Rodenstock GmbH
Priority date: 2003-09-18
Filing date: 2004-08-20
Publication date: 2006-06-07
Also published as: US20060219990A1; WO2005035529A1; JP2007505842A; US7229576B2

Abstract

The invention relates to specific photochromic phenanthropyrans and the use thereof in all types of plastics, particularly for ophthalmic purposes. The invention especially relates to photochromic compounds which are derived from 2H-phenanthro[2,1- b]pyrans and 3H-phenanthro[3,4-b]pyrans and are provided with particularly long wavelength absorption maxima in the open form while being colorless in the non-excited state.

Description

Substituted phenanthropyrans

The present invention relates to specific photochromic phenanthropyrans and their use in plastics of all kinds, in particular for ophthalmic purposes. In particular, the present invention relates to photochromic compounds derived from 2H-phenanthro [2,1-b] pyrans and 3H-phenanthro [3,4-b] pyrans, which have particularly long-wave absorption maxima in the open form, but in the non-excited state Are still colorless.

Various classes of dyes are known which reversibly change their color when irradiated with light of certain wavelengths, in particular sun rays. This is due to the fact that these dye molecules change into an excited colored state when energy is supplied in the form of light, which they leave when the energy supply is interrupted, as a result of which they return to their colorless or at least hardly colored normal state. These photochromic dyes include, for example, naphthopyrans, which have already been described in the prior art with various substituents.

Pyranes, especially naphthopyrans and larger ring systems derived from them, are photochromic compounds that have been the subject of intensive research to date. Although a patent was first registered in 1966 (US 3,567,605), it was not until the 1990s that connections could be developed that appeared suitable for use in spectacle lenses.

On the one hand, the dyes known in the prior art frequently have an insufficiently long-wave absorption in the excited as well as in the non-excited state. This also leads to problems when combined with other photochromic dyes. On the other hand, there is often too high a temperature sensitivity with regard to the darkening, and at the same time the brightening is too slow. In addition, the dyes available in the prior art often have an insufficient lifespan. As a result- however, such sun protection glasses show an insufficient durability. The latter is noticeable in rapidly declining performance and / or strong yellowing.

3H-Naphthopyrans derived from 2-naphthols and their higher analog derivatives derived therefrom by annulation are a group of photochromic dyes whose long-wave absorption maximum of the excited form is predominantly in the spectral range from 420 nm to 500 nm and thus a yellow, orange or convey a red-orange color impression (see US-A-5,869,658 and US-A-6,022,495). For neutral darkening phototropic glasses, however, powerful violet to blue photochromic dyes are required. Violet to blue photochromic dyes which are currently available in the prior art usually come from the class of the spiroxazines, fulgides or 2H-naphtho [1, 2-b] pyrans. However, spiroxazine dyes are generally disadvantageous in terms of high-temperature performance, while fulgid dyes do not have completely satisfactory properties for use in sun protection glasses in terms of the lifetime and 2H-naphtho [1, 2-b] pyrans in the brightening rate.

The introduction of electron-donating substituents on the aryl radicals in the o-position to the pyran oxygen, as described for example in WO 98/45281, WO 01/12619 and EP 0 945 451 A1, leads to red or red-violet darkening 3H-naphtho [2,1- b] pyrans. WO 01/12619 discloses compounds in which a geminal aryl group has a para-amino-substituted group and the other aryl group has an alkoxy or thioalkoxy group which is substituted in the meta or para position, this substitution pattern having a positive effect on the rate of lightening. WO 98/45281 describes red hyperchromic compounds which additionally contain an amine function primarily in the 6-position of the 3H-naphtho [2,1-b] pyran unit. Compounds with non-pronounced basic amino groups are described in EP 0 945 451 A1, which in the excited state have a pink to violet color and have an appealing service life. 3H-Naphtho [2,1-b] pyrans with Aryl substituents in the 6-position are also described in WO 99/31082. However, the effect of aryl substitution in the 6-position on the longest-wave absorption maximum of the unexcited as well as the excited form is very small with these compounds.

Corresponding substitution in the 8-position of the 3H-naphtho [2,1-b] pyran unit brings about a bathochromic shift in the longest wavelength absorption maximum, above all through the introduction of alkoxy groups, as described in US Pat. No. 5,238,981. In addition, compounds with dialkylamino groups in the 8-position are also disclosed. The use of nitrogen heterocycles as substituents in the 8-position of the 3H-naphtho [2,1-b] pyran unit is mentioned in US-A-5,990,305, which, in contrast to open-chain amino groups, achieves an improved lifespan. This is also achieved with substituents that contain so-called HALS (hindered amine light stabilizer) structural units. Finally, WO 03/055872 contains violet to blue 3H-naphtho [2,1-b] pyrans which have substituents containing amino groups both in the 3-position and 8-position, and in WO 03/080595 blue 3H- Naphtho [2,1-b] pyrans which, in addition to the above substituents in the 3- and 8-positions, have a substituent in the 6-position.

Larger aromatic ring systems containing a naphthopyran moiety are described, for example, in US-5, 106,998, US-A-5,888,432, US-A-4,826,977 and US-A-5,637,709. However, the compounds are not substituted with two aryl radicals in the 3-position, but instead have at least one saturated polycyclic substituent and thus, in the excited form, lead to yellow to red photochromic compounds.

Furthermore, US Pat. Nos. 5,565,147, 5,674,432 and 6,294,112 (WO 98/45281) (WO 98/45281) disclose photochromic 3H-naphtho [2,1-b] pyrans which have a heterocyclically fused unit on different sides of the naphthalene unit exhibit. For example, US Pat. No. 6,294,112 (WO 98/45281) describes red hyperchromic 3H-naphtho [2,1-b] pyrans, which may be heterocyclically annelated. In EP 1 038 870 A1 describes 3H-naphtho [2,1-b] pyrans which have an optionally substituted amido group in the 5-position and whose naphthopyran unit can be expanded with a heterocycle or aromatic ring.

Substituted phenanthropyrans are described in US-A-5,514,817 and US-A-6,210,608. However, these are derived from 2H-naphtho [1, 2-b] pyrans.

It is therefore the object of the present invention to provide new photochromic dyes which are colorless in the non-excited form and which differ from comparable compounds from the prior art, in particular by a favorable combination of long-wave absorption and high darkening performance with good darkening performance in the excited state Kinetic and lifetime properties, ie fast brightening speed and good behavior in the life test.

This object is achieved by the objects characterized in the claims.

In particular, photochromic 2H-phenanthro [2,1-b] pyrans according to the general formula (I) or 3H-phenanthro [3,4-b] pyrans of the general formula (II) are provided:

CD (π)

wherein m is an integer from 0 to 3,

the radicals Rj, R ₃ , R ₄ and R ₅ independently of one another represent hydrogen or a substituent selected from the group α, consisting of fluorine, chlorine, bromine, hydroxyl, silyloxy, a straight-chain or branched-chain (Ct-C ₆ ) -alkyl radical , a (C ₃ -C ₇ ) cycloalkyl radical, a straight-chain or branched (Cι-C ₆ ) alkoxy radical, phenyl, phenoxy, benzyl, benzyloxy, naphthyl, naphthoxy, phenanthryl or pyridyl, each with one, two or three substituents - ducks, independently selected from the group ß, consisting of a straight-chain or branched (CrCβJ-alkyl radical, a (C ₃ -C ₇ ) - cycloalkyl radical, a straight-chain or branched (CrC ₆ ) -alkoxy radical, hydroxy, tert-butyldiphenylsilyloxy , Amino, Di (Cι-C ₆ ) alkylamino, nitro, cyano, benzyl, 4-methoxybenzyl, 4-nitrobenzyl, phenyl, 4-methoxyphenyl, 4-dimethylaminophenyl, pyridyl and pyrimidinyl, may be substituted, or represent an NRβRr group , where the residues Rβ u nd R ₇ independently of one another from hydrogen, a straight-chain or branched-chain (C ₁ -C ₆ ) alkyl radical, a (C ₃ -C ₇ ) cycloalkyl radical, phenyl or benzyl, the latter two having one or more substituents from the group β , are selected, or the radicals Rβ and R ₇ together with the nitrogen atom form an azaadamantyl group or a 3- to 10-membered nitrogen heterocycle which may be unsubstituted or substituted by a straight-chain or branched-chain (Ci-Ce) alkyl radical, where the nitrogen heterocycle may contain one or more heteroatoms from the group O, S or NR ⁸ , the radical R ^{8 being selected} from hydrogen or the group β, and the nitrogen heterocycle being fused with one or two benzene rings; or

two adjacent radicals R ₅ together form an un-, mono- or disubstituted fused benzo ring, the substituents of which are selected independently of one another from the group α or an NR ₆ R7 group defined above; or the radical R ₃ together with the radical R ⁴ forms an un-, mono- or disubstituted fused benzo ring to form a triphenylene pyran, the substituents being selected independently of one another from the group α or a previously defined NR ₆ R ₇ group;

the radical R ₂ consists of hydrogen or a substituent from group α, an NReR7 group defined above or quinolinyl, isoquinolinyl, thienyl, benzothienyl, dibenzothienyl, furanyl, benzofuranyl, dibenzofuranyl, carbazolyl, phenothiazinyl, phenoxazinyl, oxazolyl, benzadazazolyl, benzoxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, thiadiazolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyrimidinyl, pyrazinyl, acetyl, benzoyl, cyano, formyl, iminomethyl, 1-imino aminomethyl, N-hydroxyiminomethyl, methyleneamino, cyanoamino, cyanomethyl, dicyanomethyl, carboxy, carboxymethyl, (CrCβJ-acyloxy, (-C-C ₆ ) -alkoxycarbonyl, (CrC ₆ ) -alkoxycarbonyl-methyl, phenoxycarbonyl, benzyloxycarbonyl, nitro, di-azophenyl, aminocarbonyl, ethenyl, 4-ethenylphenyl, ethynyl or 4-ethynylphenyl or to form one cationic structure from N- (CrC ₆ ) -alkylpyridinio, 1-pyridinio, N- (CrC ₆ ) -alkylquinolinio, 1-quinolinio, N- (CrC ₆ ) -alkylisoquinolinio, 2-isoquinolinio, iminiomethyl or 1-lminioaminome thyl, in which case the corresponding counterion is selected from chloride, bromide, sulfate, hydrogen sulfate, tetrafluoroborate, hexafluorophosphate, mesylate, tosylate or triflate, the above substituents, where possible, each having one, two, three or four substituents from the group β can, is selected;

or the radicals Ri and R ₂ in the formula (I) or R ₁ and R ₂ or R ₂ and R ₃ in the formula (II) are an aromatic or heteroaromatic ring fused to the phenanthrene unit, selected from a benzene ring, a pyridine ring, an indole ring, a benzofuryl ring, a benzothienyl ring, a thienyl ring, a furyl ring or a pyrimidinyl ring, which can each be substituted by one or more substituents from the group α, and where in the case of an indole ring, a benzofuryl ring or of a benzothienyl ring which anneals to the phenanthrene skeleton via the 5-membered heterocycle; or the radical R ₂ together with a radical R ₅ in the 10-position of the phenanthrene system according to formula (I) form a fused benzo ring with formation of a pyrenopyran according to formula (III) below

or forms a fused pyrido ring, the nitrogen atom then replacing the carbon atom connected to Rg or R ₁₀ , where the fused benzo ring can be substituted by the radicals Rg and R ₁₀ and the fused pyrido ring by a radical Rg, where Rg or Rg and R-to is or are selected independently of one another from the group α, or wherein the radicals Rg and R ₁₀ in the formula (III) together in turn form a fused aromatic or heteroaromatic ring selected from a benzene ring, a pyridine ring, an indole ring, one Benzofuryl ring, a benzothienyl ring, a thienyl ring, a furyl ring or a pyrimidinyl ring, which can each be substituted with one or more substituents from the group α, and where in the case of an indole ring, a benzofuryl ring or a benzothienyl ring the annulation via the 5- membered heterocycle occurs, form; and

B and B 'are selected independently of one another from un-, mono- or disubstituted phenyl, ethynyl, ethenyl, naphthyl, furanyl, benzofuranyl, thienyl, benzothienyl or julolidinyl, the substituents from the group α, one as defined above NReR ₇ group and ethenyl, 4-ethenylphenyl, ethynyl or 4-ethynylphenyl are selected, the substituents being selected from the group α and, as far as possible, the above substituents in turn can each independently have two or three substituents from the group β, or where two directly adjacent substituents represent a Y- (CH ₂ ) _q -Z grouping, where q = 1, 2 or 3 and Y and Z can be independently oxygen, sulfur, NCH ₃ , NPh, CH ₂ , C (CH ₃ ) ₂ or C (C ₆ H ₅ ) 2, or 'B and B' together form a representing mono- or disubstituiert.es 9-spirofluorene, the fluorene substituents being selected from the group ß, or B and B together represent 'is a saturated hydrocarbon, the C3-C ₁₂ spiromonocyclisch, C ₇ -C ₁₂ spirobicyclisch or C7 -Ci _{2 is} spirotricyclic.

The enlargement of the basic aromatic system by benzoannulation on the g or i side of 3H-naphtho [2,1-b] pyrans leads to 2H-phenanthro [2,1-bpyrans or 3H-phenanthro [3,4- b] pyrans, which are still colorless in the non-excited form and have a high extinction. With simultaneous introduction of corresponding substituents, which lead to a longer-wave absorption of the compounds in the excited form, and / or simultaneous introduction of corresponding substituents in the 11-position of the compounds of the formula (I) or in the 6-position of the compounds of the formula (II) the photochromic properties of the dyes, in particular their performance, can be further increased. Compared to comparable compounds from the prior art, the compounds according to the invention have a longer-wave absorption and at the same time an equally good darkening performance. In addition, the photochromic 2H-phenanthro [2,1-b] pyrans or 3H-phenanthro [3,4-b] pyrans according to the invention have a good lifespan and fast brightening speeds with an exceptional darkening performance.

m is 0 to 3, because for steric reasons there is usually no substituent in the peri position, ie 10 position, except in the above case that R ₅ together with R ₂ forms a fused benzo ring or pyrido ring. In one embodiment of the present invention, the radicals R 1, R ₃ , R ₄ and R _{5 are selected} independently of one another from hydrogen, a substituent from the group α or a —NR ₆ R ₇ group as defined above.

In a further embodiment of the present invention, at least one of the radicals B and B 'is selected from a phenyl radical which is substituted in the para position with a -NR ₆ R ₇ group as defined above. The radicals Rβ and R ₇ together with the nitrogen atom of this -NR ₆ R ₇ group can also form an azaadamantyl group. Alternatively, they can also be a 3- to 10-membered nitrogen heterocycle as defined above, in particular a morpholine group, a thiomorpholine group, a piperidine group, an azacycloheptane group, an azacyclooctane group, a 1,4-diaza-1-methylcycloheptane group, a piperazine group N- (N '- (CrC6-

Form alkyl) piperazine group or a pyrrolidine group, or the phenyl radical substituted in the para position with an -NR ₆ R ₇ group as a whole represents an N-methyl-1, 2,3,4-tetrahydroquinolinyl group bonded in the 6-position, so that the following structural unit exists:

In another embodiment, at least one of B and B 'is preferably a 4-dimethylaminophenyl group.

If one of the radicals B and B 'represents a julolidinyl radical bonded to the pyran ring via the 3-position, the following structural unit results:

In a further preferred embodiment of the present invention, the radical R ₂ in the formulas (I) and (II) is composed of (C ₁ -C ₆ ) -alkyl, phenyl, 4-methoxyphenyl, 4-dimethylaminophenyl, ethenyl, ethynyl, 2- ((C ₁ -C ₆ ) alkyl) ethenyl, 2 - ((dC ₆ ) alkyl) ethynyl, 2-phenylethenyl or 2-phenylethynyl.

In another preferred embodiment of the present invention, the radical R ₉ in the formula (III) is composed of (-C ₆ ) -alkyl, phenyl, 4-methoxyphenyl, 4-dimethylaminophenyl, ethenyl, ethynyl, 2 - ((C ₁ - C ₆ ) alkyl) ethenyl, 2 - ((C 1 -C ₆ ) alkyl) ethynyl, 2-phenylethenyl or 2-phenylethynyl selected.

Particularly preferred photochromic 2H-phenanthro [2,1-b] pyrans with the formula (I) according to the present invention have the following combination of substituents: R 1, R ₃ , R ₄ and R ₅ each represent hydrogen, R ₂ represents (CrC ₆ ) alkyl, phenyl, 4-methoxyphenyl, 4-dimethylaminophenyl, ethenyl, ethynyl, 2 - ((CC ₆ ) -alkyl) ethenyl, 2 - ((CrC ₆ ) -alkyl) ethynyl, 2-phenylethenyl or 2-phenylethynyl, B 'represents phenyl, - B is selected from 4-dimethylaminophenyl or 4- (N-azacycloheptyl) phenyl.

Particularly preferred photochromic pyrenopyrans with the formula (III) according to the present invention have the following combination of substituents: R 1, R ₃ , R ₄ and R ₅ each represent hydrogen, R ₂ represents (CC ₆ ) alkyl, phenyl, 4-methoxyphenyl, 4-dimethylaminophenyl, ethenyl, ethynyl, 2 - ((CC ₆ ) alkyl) ethenyl, 2 - ((CrC ₆ ) alkyl) ethynyl, 2- Is phenylethenyl or 2-phenylethynyl, B 'is phenyl, B is selected from 4-dimethylaminophenyl or 4- (N-azacycloheptyl) phenyl.

The longest-wave absorption maxima of the open (colored) form of exemplary compounds according to formula (I) are given in the table below:

λmax: Longest-wave absorption maximum of the open (colored) form [measured in methacrylate polymer]

The longest wave absorption maxima of the open (colored) form of exemplary compounds according to formula (III) are given in the table below:

The compounds according to the invention can be used in plastic materials or plastic objects of any type and shape for a large number of uses. purposes for which photochromic behavior is important. A dye according to the present invention or a mixture of such dyes can be used. For example, the photochromic 2H-phenanthro [2,1-b] pyrans or 3H-phenanthro [3,4-bjpyrane according to the invention can be used in lenses, in particular ophthalmic lenses, glasses for glasses of all kinds, such as, for example, ski goggles, sunglasses, motorcycle glasses, visors from Protective helmets, and the like are used. Furthermore, the photochromic dyes according to the invention can also be used, for example, as sun protection in vehicles and living spaces in the form of windows, protective covers, covers, roofs or the like.

To produce such photochromic articles, the photochromic 2H-phenanthro [2,1-b] pyran or 3H-phenanthro [3,4-b] pyran dyes according to the invention can be prepared by various processes described in the prior art, such as already stated in WO 99/15518, applied to a polymer material, such as an organic plastic material, or embedded therein.

A distinction is made between so-called mass coloring and surface coloring processes. A bulk dyeing process includes, for example, dissolving or dispersing the photochromic compound or compounds according to the present invention in a plastic material, for example by adding the photochromic compound (s) to a monomeric material before the polymerization takes place. Another possibility for producing a photochromic object is the penetration of the plastic material (s) with the photochromic compound (s) by immersing the plastic material in a hot solution of the photochromic dye or dyes according to the present invention or, for example, also a thermal transfer process. The photochromic compound (s) can also be provided, for example, in the form of a separate layer between adjacent layers of the plastic material, for example as part of a polymeric film. It is also possible to apply the photochromic compound (s) as part of a coating on the surface of the plastic material. The expression "Penetration" is intended to mean the migration of the photochromic compound (s) into the plastic material, for example through the solvent-assisted transfer of the photochromic compound (s) into a polymer matrix, vapor phase transfer or other such surface diffusion processes. Such photochromic objects, such as, for example, spectacle lenses, can advantageously be produced not only by means of the customary mass coloring, but also in the same way by means of surface coloring, with the latter variant being able to achieve a surprisingly lower tendency to migrate. This is particularly advantageous in subsequent finishing steps, since - for example with an anti-reflective coating due to the lower back diffusion in the vacuum - layer detachments and similar defects are drastically reduced.

Overall, on the basis of the photochromic 2H-phenanthro [2,1-b] pyran or 3H-phenanthro [3,4-b] pyran dyes according to the invention, any compatible (chemically and color-compatible) colorations, i.e. Dyes applied to or embedded in the plastic material in order to satisfy both aesthetic and medical or fashion aspects. The specific dye (s) selected can therefore vary depending on the intended effects and requirements.

The photochromic 2H-phenanthro [2,1-b] pyran dyes according to the invention with the general formula (I) or such derivatives with the formula (III) can be prepared, for example, according to the reaction scheme shown in FIG.

The key step in the synthesis of the compounds according to the invention are cyclizations based on the corresponding 1,3-diketone or 1,3,5-triketone derivatives, i.e. 4- (2-naphthyl) butane-1,3-dione derivatives or 6- (2-naphthyl) hexane-1,3,5-trione derivatives, using phosphoric acid at approx. 100 ° C. The hydroxyphenanthrene or hydroxypyrene derivatives thus obtained are then reacted with suitably substituted 2-propyne-1-ol derivatives to give the compounds of the invention.

Claims

Expectations

1. Photochromic phenanthropyran compound according to general formula (I) or general formula (II):

(I) CD) wherein m is an integer from 0 to 3, the radicals R 1, R ₃ , R ₄ and R ₅ independently of one another represent hydrogen or a substituent selected from the group α, consisting of fluorine, chlorine, bromine, Hydroxy, silyloxy, a straight-chain or branched-chain (Cι-Ce) -alkyl radical, a (C ₃ -C ₇ ) -cycloalkyl radical, a straight-chain or branched-chain (C-ι-C ₆ ) -alkoxy radical, phenyl, phenoxy, benzyl, benzyloxy, Naphthyl, naphthoxy, phenanthryl or pyridyl, each with one, two or three substituents, independently selected from the group β, consisting of a straight-chain or branched-chain (-C-C ₆ ) -alkyl radical, a (C ₃ -C ₇ ) - Cycloalkyl radical, a straight-chain or branched-chain (-C-C ₆ ) alkoxy radical, hydroxy, tert-butyldiphenylsilyloxy, amino, di (-C-C ₆ ) alkylamino, nitro, cyano, benzyl, 4-methoxybenzyl, 4-nitrobenzyl, phenyl, 4 -Methoxyphenyl, 4-dimethylaminophenyI, pyridyl and pyrimidinyl, may be substituted, or egg represent a NR ₆ R ₇ group, the radicals RQ and R ₇ independently of one another consisting of hydrogen, a straight-chain or branched-chain (CC ₆ ) alkyl radical, a (C ₃ -C ₇ ) - Cycloalkyl, phenyl or benzyl, where the latter two may have one or more substituents from the group β, are selected, or the radicals R_ and R ₇ together with the nitrogen atom form an azaadamantyl group or a 3- to 10-membered nitrogen heterocycle which is unsubstituted or can be substituted with a straight-chain or branched-chain (-C-C _. ) alkyl radical, where the nitrogen heterocycle can contain one or more heteroatoms from the group O, S or NR ⁸ , the radical R ^{8 being selected} from hydrogen or the group β , and wherein the nitrogen heterocycle can be fused with one or two benzene rings; or

two adjacent radicals R ₅ together form an un-, mono- or disubstituted fused benzo ring, the substituents of which are selected independently of one another from the group or from an NReR ₇ group defined above; or

the radical R ₃ together with the radical R ⁴ forms an un-, mono- or disubstituted fused benzo ring to form a triphenylene pyran, the substituents being selected independently of one another from the group α or an NReR ₇ group defined above;

the radical R ₂ consists of hydrogen or a substituent from group α, an NReR ₇ group defined above or quinolinyl, isoquinolinyl, thienyl, benzothienyl, dibenzothienyl, furanyl, benzofuranyl, dibenzofuranyl, carbazolyl, phenothiazinyl, phenoxazinyl, oxazolyl, benzoxazolyl, benzoxazolyl .

Thiazolyl, benzothiazolyl, thiadiazolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyrimidinyl, pyrazinyl, acetyl, benzoyl, cyan, formyl, iminomethyl, 1-imino-aminomethyl, N-hydroxyiminomethyl, methyleneamino, cyanoamoxy, cyanamino, cyanamino, cyanamino, cyanamino, cyanamino, cyanamino, cyanamino, cyanamino, cyanamino, cyanamino, cyanamino, cyano Carboxymethyl, (-CC ₆ ) -acyloxy, (CC ₆ ) alkoxycarbonyl, (CrC ₆ ) alkoxycarbonyl-methyl, phenoxycarbonyl, benzyloxycarbonyl, nitro, diazophenyl, aminocarbonyl, ethenyl, 4-ethenylphenyl, ethynyl or 4-ethynylphenyl or with the formation of a tional structure of N- (-C-C ₆ ) -alkylpyridinio, 1-pyridinio, N- (Cι-C ₆ ) -alkylquinolinio, 1-quinolinio, N- (-C-C ₆ ) -alkylisoquinolinio, 2-isoquinolinio, imi- niomethyl or 1-lminioaminomethyl, in which case the corresponding counter ion is selected from chloride, bromide, sulfate, hydrogen sulfate, tetrafluoroborate, hexafluorophosphate, mesylate, tosylate or triflate, the above substituents, where possible, in each case one, two, three or four May have substituents from the group β is selected;

or the radicals Ri and R ₂ in the formula (I) or Ri and R ₂ or R ₂ and R3 in the formula (II) are an aromatic or heteroaromatic ring fused to the phenanthrene unit, selected from a benzene ring, a pyridine ring, an indole ring, a benzofuryl ring, a benzothienyl ring, a thienyl ring, a furyl ring or a pyrimidinyl ring, which can each be substituted by one or more substituents from the group α, and in the case of an indole ring, a benzofuryl ring or a benzothienyl ring the annealing to the Phenanthrene skeleton occurs over the 5-membered heterocycle, form; or

the radical R ₂ together with a radical R ₅ in the 10-position of the phenanthene system according to formula (I) form a fused benzo ring with formation of a pyrenopyran according to formula (III) below

or forms a fused pyrido ring, the nitrogen atom then replacing the carbon atom connected to Rg or Rio, where the fused benzo ring can be substituted by the radicals Rg and Rio and the fused pyrido ring by a radical Rg, where Rg or Rg and Rι ₀ is independently selected from the group α, or the radicals Rg and Rio in the formula (III) together in turn form a fused aromatic or heteroaromatic ring selected from a benzene ring, a pyridine ring, an indole ring, a benzofuryl ring, a benzothienyl ring , a thienyl ring, a furyl ring or a pyrimidinyl ring, each of which can be substituted with one or more substituents from the group α, and in the case of an indole ring, a benzofuryl ring or a benzothienyl ring the annealing takes place via the 5-membered heterocycle, form; and

B and B 'are independently selected from unsubstituted, mono- or di-substituted phenyl, ethynyl, ethenyl, naphthyl, furanyl, benzofuranyl, thienyl, benzothienyl + 6 or julolidinyl, the substituents being selected from the group α, an NR as defined above ₆ R ₇ group and ethenyl, 4-ethenylphenyl, ethynyl or 4-ethynylphenyl are selected, the substituents from the group α and the above substituents, as far as possible, again each independently having two or three substituents from the group β can, or where two directly adjacent substituents represent a Y- (CH ₂ ) _q -Z grouping, where q = 1, 2 or 3 and Y and Z independently of one another oxygen, sulfur, NCH ₃ , NPh, CH ₂ , C (CH ₃ ) ₂ or C (C ₆ H ₅ ) 2, or

B and B 'together represent an unsubstituted, mono- or disubstituted 9-spirofluorene, the fluorene substituents being selected from the group β, or B and B' together represent a saturated hydrocarbon which is C ₃ -

C ₁ 2 is spiromonocyclic, C7-C ₁ 2 spirobicyclic or C ₇ -C ₁₂ spirotricyclic.

2. A compound according to claim 1, wherein at least one of the radicals B and B 'is selected from a phenyl radical which is substituted in the para position with a -NR ₆ R ₇ group as defined above.

3. A compound according to claim 1 or 2, wherein the -NR ₆ R ₇ group in its entirety for diphenylamino, dianisylamino, morpholinyl, thiomorpholinyl, 3,5-dimethylthiomorpholinyl, piperidinyl, azacycloheptyl, azacyclooctyl, 1,4-diaza-1-methyl -cycloheptyl, piperazinyl, pyrrolidinyl or 1, 2,3,4-tetrahydroisoquinolinyl.

4. A compound according to any one of claims 1 to 3, wherein the radical R ₂ in the formulas (I) and (II) from (-C-C ₆ ) alkyl, phenyl, 4-methoxyphenyl, 4-dimethylaminophenyl, ethenyl, ethynyl, 2 - ((CrC ₆ ) alkyl) ethenyl, 2 - ((CC ₆ ) alkyl) ethynyl, 2-phenylethenyl or 2-phenylethynyl is selected.

5. A compound according to any one of claims 1 to 3, wherein the radical Rg in the formula (III) from (-C-C ₆ ) alkyl, phenyl, 4-methoxyphenyl, 4-dimethylaminophenyl, ethenyl, ethynyl, 2 - ((CrC ₅ ) -alkyl) ethenyl, 2 - ((CC ₆ ) -alkyl) ethynyl, 2-phenylethenyl or 2-phenylethynyl is selected.

6. A compound according to any one of claims 1 to 5, wherein with respect to compounds according to formula (I) R 1, R ₃ , R ₄ and R ₅ each represent hydrogen, R ₂ (-CC ₆ ) alkyl, phenyl, 4-methoxyphenyl, 4-Dimethylaminophenyl, ethenyl, ethinyl, 2 - ((CC ₆ ) -alkyl) ethenyl, 2 - ((-C-C ₆ ) -alkyl) ethynyl, 2-phenylethenyl or 2-phenylethynyl, B 'is phenyl and B is from 4- dimethylaminophenyl or 4- (N-azacycloheptyl) phenyl is selected.

7. A compound according to any one of claims 1 to 5, wherein with respect to compounds according to formula (III) R ₁ , R ₃ , R ₄ and R ₅ each represent hydrogen, R ₂ (-CC ₆ ) alkyl, phenyl, 4-methoxyphenyl , 4-dimethylaminophenyl, ethenyl, ethynyl, 2 - _((C-C6) alkyl) ethenyl, 2 - ((CC ₆₎ alkyl) ethynyl, represents 2-phenylethenyl or 2-phenylethynyl, B 'is phenyl and B is selected from 4-dimethylaminophenyl or 4- (N-azacycloheptyl) phenyl.

8. Use of the photochromic compounds according to one of claims 1 to 7 in plastic materials.

9. Use according to claim 8, wherein the plastic material is an ophthalmic lens.