Naphthopyran derivatives, compositions and (co) polymer...

Details Naphthopyran derivatives, compositions and (co) polymer... Naphthopyran derivatives, compositions and (co) polymer...

1999-07-20

2002-06-04

Solola, T. A. (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C514S454000, C359S241000

Reexamination Certificate

active

06399791

ABSTRACT:

The present invention relates to novel compounds, naphthopyran derivatives, which possess, in particular, photochromic properties. It relates also to photochromic compositions and photochromic ophthalmic articles (for example lenses) containing said novel compounds.
The photochromic compounds are able to change color under the influence of a poly- or monochromatic light (for example UV) and to regain their initial color when the light irradiation ceases, or under the influence of temperature and/or of poly- or monochromatic light different from the first.
The photochromic compounds find applications in various fields, for example for the manufacture of ophthalmic lenses, contact lenses, solar protection lenses, filters, camera optical systems or photographic apparatus optical systems or optical systems of other optical devices, and observation optical systems, glazings, decorative objects, bill elements or even for the storage of information by optical inscription (coding).
In the field of ophthalmic optics, and in particular in the spectacles trade, a photochromic lens, comprising one or more photochromic compounds, must possess:
a high transmission in the absence of ultraviolets,
a low transmission (high colorability) under solar irradiation,
adapted coloration and discoloration kinetics,
a tint acceptable to the consumer (gray or brown, preferably) with, preferably, a maintenance of the chosen tint during coloration and discoloration of the lens,
a maintenance of the performances, i. e. the properties in a temperature range of 0-40° C.,
an important durability, since these desired objectives are sophisticated corrective lenses and are therefore expensive.
These lens characteristics are, in fact, determined by the active photochromic compounds that it contains; these compounds must in addition be perfectly compatible with the organic or inorganic support making up the lens.
It is in other respects to be noted that obtaining a gray or brown tint may necessitate the use of at least two photochromes of different colors, i.e. having distinct maximal absorption wavelengths in the visible. This association further imposes other requirements of the photochromic compounds. In particular, the coloration and discoloration kinetics of the (two or more) associated active photochromic compounds must be roughly identical. The same applies for their stability with time and, also, the same applies for their compatibility with a plastic or inorganic support.
Among the numerous photochromic compounds described in the prior art, benzopyrans or naphthopyrans described in the patents U.S. Pat. No. 3,567,605, U.S. Pat. No. 3,627,690, U.S. Pat. No. 4,818,096, U.S. Pat. No. 4,826,977, U.S. Pat. No. 5,200,116, U.S. Pat. No. 5,238,981, U.S. Pat. No. 5,458,814 and in the Research Disclosure No. 36144, may be cited, which are of the following formula:
These compounds claim to satisfy the specifications defined above. In reality, if these compounds really have one or more of the basic properties sought after, such as a high transmission in the absence of ultraviolets and a high colorability under solar irradiation, all the compounds described hitherto have not the complete combination of properties sought after which are necessary for the production of satisfactory articles which can be manufactured industrially.
It is to the credit of the Applicant to have found, in a surprising way, that the presence of a group of the type —C(R1)(R2)(OR3) in position 5 of 2H-naphtho[1,2-b]pyrans enabled lowering their discoloration kinetics. This type of molecules, novel per se, adapts well in association with yellow and/or orange and/or red complementary photochromes in order to give gray or brown tints.
The present invention thus has, for first subject, naphthopyran derivatives of formula:
optionally substituted in position(s) 2, 3, 4, 6, 7, 8, 9 or/and 10; the substituent Z in position 5 being of formula —C(R1)(R2)(OR3) in which:
R1 and R2, identical or different represent independently: hydrogen or a linear alkyl group having 1 to 6 carbon atoms;
R3 represents:
hydrogen,
an R11 group, R11 representing:
a linear or branched alkyl group having 1 to 12 carbon atoms;
a cycloalkyl or bicycloalkyl group having 3 to 12 carbon atoms;
an aralkyl group, the alkyl group, linear or branched, having 1 to 3 carbon atoms and the aryl group being selected from a phenyl group or a naphthyl group optionally substituted with at least one linear or branched alkyl group having 1 to 6 carbon atoms or a linear or branched alkoxy group having 1 to 6 carbon atoms;
a CH
2
CO(R12) group, R12 being an OH, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a phenoxy group;
a CH
2
CN group;
a CO(R13) group, R13 representing:
a linear or branched alkyl group, having 1 to 12 carbon atoms;
a cycloalkyl or bicycloalkyl group having 3 to 12 carbon atoms;
a vinyl or 2-propenyl group (having therefore OR
3
═OCOR
13
which represents respectively an acryloyl or methacryloyl group);
a phenyl or naphthyl group optionally substituted with at least one linear or branched alkoxy group having 1 to 6 carbon atoms;
a phenoxy group;
a secondary amine group NH(R14), R14 representing a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group optionally substituted with at least one linear or branched alkyl group having 1 to 6 carbon atoms.
Said naphthopyran derivatives include the naphthopyran substituted in position 5 with Z, as well as all the other compounds of corresponding formulae, which have at least one substituent on the —CH and —CH
2
groups of the formula below. Among said derivatives, those which are disubstituted on the carbon a to oxygen of the pyran ring are preferred. Said a carbon may therefore be an asymmetric carbon. The compounds of the invention may therefore be in the form of racemic mixtures (generally) or they may be pure isomers of such derivatives having an asymmetric carbon.
In the context of its first subject, such as defined above, the present application relates to naphthopyran derivatives of formula (I) below:
wherein:
R1, R2 and R3 are such as defined above;
R4 to R8, identical or different, represent independently:
hydrogen;
a halogen, notably fluorine, chlorine or bromine;
a linear or branched alkyl group having 1 to 12 carbon atoms;
a linear or branched alkoxy group having 1 to 12 carbon atoms;
a linear or branched alkenyl group having from 1 to 12 carbon atoms, notably a vinyl or allyl group;
an aryl or heteroaryl group having 6 to 24 carbon atoms or 4 to 24 carbon atoms respectively in its basic structure and at least one heteroatom selected from sulfur, oxygen and nitrogen; said basic structure being optionally substituted with at least one substituent selected from:
a halogen, notably fluorine, chlorine and bromine;
a linear or branched alkyl group having 1 to 6 carbon atoms;
a linear or branched alkoxy group having 1 to 6 carbon atoms;
a linear or branched haloalkyl or haloalkoxy group having 1 to 6 carbon atoms, notably a fluoroalkyl group of this type;
an —NH
2
group;
an —NHR group, R representing a linear or branched alkyl group having 1 to 6 carbon atoms;
a
 group, R′ and R″, which are identical or different, representing independently a linear or branched alkyl group having 1 to 6 carbon atoms or, together with the nitrogen atom to which they are attached, form a 5 to 7 membered ring which may have at least one other heteroatom selected from oxygen, sulfur and nitrogen, said nitrogen being optionally substituted with an R′″ group which is a linear or branched alkyl group having 1 to 6 carbon atoms;
an amine or amide group: —NH
2
, —NHR, —CONH
2
, —CONHR,
 R, R′, R″ being respectively of their definitions given above for the amine substituents of the values R4 to R8: aryl or heteroaryl;
a —OCO(R15) or —COO(R15) group, R15 representing a linear or branched alkyl group having 1 to 6 carbon atoms, a cycloalkyl group

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