Photochromic fluorenopyrans with defined dibenzo[B,D]pyrano fused attachment

Patent metadata

Field	Value
Publication number	US-9963574-B2
Application number	US-201314413758-A
Country	US
Kind code	B2
Filing date	Jul 11, 2013
Priority date	Jul 12, 2012
Publication date	May 8, 2018
Grant date	May 8, 2018

Abstract

The present invention relates to photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion in accordance with general formulae (I) or (II) and to their use in plastics of all kinds, particularly for ophthalmic purposes. The photochromic compounds of the invention are distinguished by two pronounced absorption bands of the open form in the visible wavelength range, meaning that with dye molecules of this kind it is possible to replace two conventional photochromic dyes each having only one discrete absorption band. The compounds of the invention, moreover, have a very good lifetime with very high performance.

First claim

The invention claimed is:

1. Photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion in accordance with the general formulae (I) or (II):

where for the radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are:
(i) each independently of one another are a substituent group α selected from a hydrogen atom, a (C 1 -C 6 )-alkyl radical, a (C 1 -C 6 )-thioalkyl radical, a (C 3 -C 7 )-cycloalkyl radical, which optionally contain one or more heteroatoms chosen from O or S, a (C 1 -C 6 )-alkoxy radical, a hydroxyl group, a trifluoromethyl group, bromine, chlorine, fluorine, and an unsubstituted or mono- or disubstituted phenyl, phenoxy, benzyl, benzyloxy, naphthyl, or naphthoxy radical, the substituents of the mono- or disubstituted phenyl, phenoxy, benzyl, benzyloxy, naphthyl, or naphthoxy radical are chosen from (C 1 -C 6 )-alkyl, (C 1 -C 6 )-alkoxy, bromine, chlorine, or fluorine; or
(ii)
(a) the radicals R 1 and R 2 together with the carbon atom bonded to the R 1 and R 2 radicals form a 3- to 8-membered, carbocyclic or heterocyclic ring which optionally (1) carries one or more-substituents chosen from the group α, or (2) has one to three aromatic or heteroaromatic ring systems fused thereto, the one to three aromatic or heteroaromatic ring systems being selected independently of one another from group β consisting of benzene, naphthalene, phenanthrene, pyridine, quinoline, furan, thiophene, pyrrole, benzofuran, benzothiophene, indole, and carbazole, which may be substituted in turn by one or more substituents selected from group α, and, if two of the α substituents carried on the 3- to 8-membered carbocyclic or heterocyclic ring formed by the R 1 and R 2 radicals are located on the same ring carbon atom, they may in turn form a 3- to 8-membered carbocyclic or heterocyclic ring, and/or
(b) the radicals R 5 and R 6 , together with the carbon atom bonded to the R 5 and R 6 radicals, form a 3- to 8-membered carbocyclic or heterocyclic ring which optionally (1) carries one or more-substituents chosen from the group α, or (2) has one to three aromatic or heteroaromatic ring systems fused thereto, the one to three aromatic or heteroaromatic ring systems being selected independently of one another from group β consisting of benzene, naphthalene, phenanthrene, pyridine, quinoline, furan, thiophene, pyrrole, benzofuran, benzothiophene, indole, and carbazole, which may be substituted in turn by one or more substituents selected from group α, and, if two of the α substituents carried on the 3- to 8-membered carbocyclic or heterocyclic ring formed by the R 5 and R 6 radicals are located on the same ring carbon atom, they may in turn form a 3- to 8-membered carbocyclic or heterocyclic ring, and/or
(c) two adjacent radicals R 3 form a fused benzene ring, which may be unsubstituted or mono- or disubstituted, in which case the substituents may be selected in turn from group α; and/or
(d) two adjacent radicals R 7 form a fused benzene ring, which may be unsubstituted or mono- or disubstituted, in which case the substituents may be selected in turn from group α; and when any of (iia-iid) are present, the remaining R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , or R 8 groups are independently chosen from α;

m and n independently of one another are an integer from 1 to 4,
and B and B′ independently of one another are selected from one of the following groups a) or b), where
a) are mono-, di-, and trisubstituted aryl radicals, where the aryl radical is selected from phenyl, naphthyl, or phenanthryl;
b) are unsubstituted, mono- and disubstituted heteroaryl radicals, the heteroaryl radical being selected from pyridyl, furanyl, benzofuranyl, thienyl, benzothienyl, 1,2,3,4-tetrahydrocarbazolyl or julolidinyl,
the substituents of the aryl or heteroaryl radicals in a) and b) being substituents selected from the group:
(i) α,
(ii) group χ consisting of amino, mono-(C 1 -C 6 )-alkylamino, di-(C 1 -C 6 )-alkylamino, mono- and diphenylamino unsubstituted or mono- or disubstituted on the phenyl ring, piperidinyl, N-substituted piperazinyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, indolinyl, morpholinyl, 2,6-dimethylmorpholinyl, thiomorpholinyl, azacycloheptyl, azacyclooctyl, unsubstituted or mono- or disubstituted phenothiazinyl, unsubstituted or mono- or disubstituted phenoxazinyl, unsubstituted or mono- or disubstituted 1,2,3,4-tetrahydroquinolinyl, unsubstituted or mono- or disubstituted 2,3-dihydro-1,4-benzoxazinyl, unsubstituted or mono- or disubstituted 1,2,3,4-tetrahydroisoquinolinyl, unsubstituted or mono- or disubstituted phenazinyl, unsubstituted or mono- or disubstituted carbazolyl, unsubstituted or mono- or disubstituted 1,2,3,4-tetrahydrocarbazolyl and unsubstituted or mono- or disubstituted 10,11-dihydrodibenzo[b,f]azepinyl, the substituent or substituents of the mono- or disubstituted groups in the group α or group χ being independently selected from (C 1 -C 6 )-alkyl, (C 1 -C 6 )-alkoxy, bromine, chlorine, or fluorine; or
(iii) where two directly adjacent substituents of the aryl or heteroaryl radicals in a) and b) are a V—(CR 8 R 9 ) p —W moiety, where p is 1, 2 or 3, the radicals R 8 and R 9 each independently of one another are a substituent selected from group α, and V and W independently of one another may be —O—, —S—, —N(C 1 -C 6 )alkyl)-, —N(C 6 H 5 )—, —CH 2 —, —C(CH 3 ) 2 —, or —C(C 6 H 5 ) 2 —, optionally two or more adjacent CR 8 R 9 units of this V—(CR 8 R 9 ) p —W moiety are part of a benzene ring fused thereto, optionally the benzene ring in each case contains in turn one or more substituents selected from group α, or V or W, together with the respectively adjacent CR 8 R 9 unit, are a fused benzene ring, which may be unsubstituted or mono- or disubstituted, the substituents thereof are selected from group α.

2. The photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion as claimed in claim 1 , where the radicals R 1 and R 2 independently of one another are selected from a hydrogen atom, a (C 1 -C 6 )-alkyl radical, or a (C 3 -C 7 )-cycloalkyl radical.

3. The photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion as claimed in claim 1 , where R 1 and R 2 , together with the carbon atom bonded to these radicals, form a 5- to 7-membered carbocyclic or heterocyclic ring which optionally carries one or more substituents from group α.

4. The photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion as claimed in claim 1 , where R 5 and R 6 independently of one another are selected from a hydrogen atom, a (C 1 -C 6 )-alkyl radical, or a (C 3 -C 7 )-cycloalkyl radical.

5. The photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion as claimed in claim 1 , which have the general formula (I).

6. The photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion as claimed in claim 1 , which have the general formula (III) below:

7. The photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion as claimed in claim 1 , where the radicals B and B′ independently of one another are selected from the group a).

8. A plastic material comprising one or more of the photochromic fluorenopyrans with defined dibenzo[b,d]pyrano fusion as claimed in claim 1 .

9. The plastic material of claim 8 , wherein the plastic material is an ophthalmic lens.

Assignees

• Weigand Udo
• Rohlfing Yven
• Zinner Herbert
• Rodenstock Gmbh

Inventors

• Weigand Udo
• Rohlfing Yven
• Zinner Herbert

Classifications

• G02C7/102

  Photochromic filters · CPC title

• C07D311/94

  condensed with rings other than six-membered or with ring systems containing such rings · CPC title

• C07D493/06

  Peri-condensed systems · CPC title

• G02B1/041

  Lenses · CPC title

• C08K5/1545 Primary

  Six-membered rings · CPC title