UV-curing-compatible photochromic fused naphthopyrans

Patent metadata

Field	Value
Publication number	US-10077274-B2
Application number	US-201414899389-A
Country	US
Kind code	B2
Filing date	Jun 12, 2014
Priority date	Jun 17, 2013
Publication date	Sep 18, 2018
Grant date	Sep 18, 2018

Abstract

The present invention relates to UV-curing-compatible photochromic single- or double-fused naphthopyrans of the general formulae (I) or (II) and the use thereof in plastics of all kinds, particularly for ophthalmic purposes. The photochromic compounds according to the invention are characterized by their excellent UV-curing compatibility, i.e. they remain undamaged—incorporated, for example, in an acrylate monomer matrix with UV initiator—by a free-radical polymerization of the matrix initiated by strong UV light. The photochromic dyes according to the invention, by means of suitable choice of substituents, are in addition characterized by two distinct absorption bands of the open form in the visible wavelength range, i.e. two conventional photochromic dyes, each having one discrete absorption band, can be replaced with a molecule of this type.

First claim

The invention claimed is:

1. A photochromic fused naphthopyran according to the general formula (III):

where the residue R 1 is a (C 1 -C 6 )-alkyl residue or a phenyl residue;
the residue R 3 is hydrogen, a (C 1 -C 6 )-alkyl residue or a phenyl residue; and
and where B and B′ are mutually independently selected from one of the following groups a) or b), where
a) is an unsubstituted, mono-, di- and trisubstituted aryl residue, wherein the aryl residue is phenyl, naphthyl or phenanthryl and
b) is an unsubstituted, mono- and disubstituted heteroaryl residue, wherein the heteroaryl residue is pyridyl, furanyl, thienyl, benzofuranyl, benzothienyl, 1,2,3,4-tetrahydrocarbazolyl and julolidinyl;
wherein the substituents of the aryl and heteroaryl residues in a) and b) are selected from the group α consisting of a hydrogen atom, a (C 1 -C 6 )-alkyl residue, a (C 1 -C 6 )-thioalkyl residue, a (C 3 -C 7 )-cycloalkyl residue which may have one or more heteroatoms such as O or S, a (C 1 -C 6 )-alkoxy residue, a hydroxyl group, a trifluoromethyl group, bromine, chlorine, fluorine, an unsubstituted, mono- or disubstituted phenyl, phenoxy, benzyl, benzyloxy, naphthyl or naphthoxy residue, or from the group χ consisting of amino, mono-(C 1 -C 6 )-alkylamino, di-(C 1 -C 6 )-alkylamino, phenethenyl unsubstituted, mono- or disubstituted on the phenyl ring, unsubstituted, mono- or disubstituted (phenylimino)methylene, unsubstituted, mono- or disubstituted (phenylmethylene)imino and unsubstituted, mono- or disubstituted mono- and diphenylamino, piperidinyl, 3,5-dimethylpiperidinyl, N-substituted piperazinyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, indolinyl, morpholinyl, 2,6-dimethylmorpholinyl, thiomorpholinyl, azacycloheptyl, azacyclooctyl, unsubstituted, mono- or disubstituted phenothiazinyl, unsubstituted, mono- or disubstituted phenoxazinyl, unsubstituted, mono-, di- or trisubstituted 9,10-dihydroacridinyl, unsubstituted, mono- or disubstituted 1,2,3,4-tetrahydroquinolinyl, unsubstituted, mono- or disubstituted 2,3-dihydro-1,4-benzoxazinyl, unsubstituted, mono- or disubstituted 1,2,3,4-tetrahydroisoquinolinyl, unsubstituted, mono- or disubstituted phenazinyl, unsubstituted, mono- or disubstituted carbazolyl, unsubstituted, mono- or disubstituted 1,2,3,4-tetrahydrocarbazolyl and unsubstituted, mono- or disubstituted 10,11-dihydrodibenz[b,f]azepinyl, wherein the substituent(s) may in turn be mutually independently selected from the group α;
or wherein two directly adjacent substituents of the aryl and heteroaryl residues in a) and b) are a V—(CR 8 R 9 ) p —W moiety, where p=1, 2 or 3, the residues R 8 and R 9 are each mutually independently a substituent selected from the group α, and also V and W are mutually independently selected from the moieties —O—, —S—, —N(C 1 -C 6 )-alkyl, —NC 6 H 5 -, —CH 2 —, —C(CH 3 ) 2 —or —C(C 6 H 5 ) 2 —;
or two or more adjacent —CR 8 R 9 moieties are part of a fused benzene ring, which may be unsubstituted, mono- or disubstituted, wherein the substituents may in turn be selected from the group α;
or V and/or W together with the respective adjacent —CR 8 R 9 moiety is a fused benzene ring, which may be unsubstituted, mono- or disubstituted, wherein the substituents may in turn be selected from the group α.

2. The photochromic fused naphthopyran as claimed in claim 1 , which are:
3,3-bis(4-methoxyphenyl)-6,7-ethylenedioxy-13-phenyl-14-methyl-13,14-dihydro-naphtho[2,1-d]naphtho[1,2-b]pyran;
3,3-bis(4-methoxyphenyl)-6,7-ethylenedioxy-13-phenyl-13,14-dimethyl-13,14-dihydro-naphtho[2,1-d]naphtho[1,2-b]pyran;
3,3-bis(4-ethoxyphenyl)-6,7-ethylenedioxy-13-phenyl-14-methyl-13,14-dihydro-naphtho[2,1-d]naphtho[1,2-b]pyran;
3,3-bis(4-ethoxyphenyl)-6,7-ethylenedioxy-13-phenyl-13,14-dimethyl-13,14-dihydro-naphtho[2,1-d]naphtho[1,2-b]pyran;
3-(4-methoxyphenyl)-3-phenyl-6,7-ethylenedioxy-13-phenyl-14-methyl-13,14-dihydro-naphtho[2,1-d]naphtho[1,2-b]pyran;
3-(4-methoxyphenyl)-3-phenyl-6,7-ethylenedioxy-13-phenyl-13,14-dimethyl-13,14-dihydro-naphtho[2,1-d]naphtho[1,2-b]pyran;
3-(4-ethoxyphenyl)-3-phenyl-6,7-ethylenedioxy-13-phenyl-14-methyl-13,14-dihydro-naphtho[2,1-d]naphtho[1,2-b]pyran;
3-(4-ethoxyphenyl)-3-phenyl-6,7-ethylenedioxy-13-phenyl-13,14-dimethyl-13,14-dihydro-naphtho[2,1-d]naphtho[1,2-b]pyran;
3-(4-butoxyphenyl)-3-phenyl-6,7-ethylenedioxy-13-phenyl-14-methyl-13,14-dihydro-naphtho[2,1-d]naphtho[1,2-b]pyran; or
3-(4-butoxyphenyl)-3-phenyl-6,7-ethylenedioxy-13-phenyl-13,14-dimethyl-13,14-dihydro-naphtho[2,1-d]naphtho[1,2-b]pyran.

3. The photochromic fused naphthopyran as claimed in claim 1 , wherein the residues B and B′ are mutually independently selected from the group a), as defined above.

4. A plastic material comprising the photochromic fused naphthopyran as claimed in claim 1 , wherein the photochromic material is disposed in the plastic material, disposed in a coating on a surface of the plastic material, or provided as a separate layer disposed between adjacent layers of the plastic material.

5. The plastic material as claimed in claim 4 , wherein the plastic material is an ophthalmic lens.

Assignees

• Rodenstock Gmbh

Inventors

• Weigand Udo
• Zinner Herbert
• Rohlfing Yven

Classifications

• G02C7/102

  Photochromic filters · CPC title

• C08K5/1575

  Six-membered rings · CPC title

• G02B5/23

  Photochromic filters · CPC title

• C07D493/04 Primary

  Ortho-condensed systems · CPC title

• G02C7/022

  Ophthalmic lenses having special refractive features achieved by special materials or material structures (G02C7/049 takes precedence) · CPC title