Photochromic multiple ring-fused naphthopyrans having extreme longwave absorption extending far into the visible wavelength range

Patent metadata

Field	Value
Publication number	US-10647852-B2
Application number	US-201716336185-A
Country	US
Kind code	B2
Filing date	May 23, 2017
Priority date	Sep 26, 2016
Publication date	May 12, 2020
Grant date	May 12, 2020

Abstract

The present invention relates to photochromic polyfused naphthopyrans having very long-wave absorption of the closed form extending well into the visible wavelength range, and to the use thereof in all kinds of plastics, especially for ophthalmic purposes, preferably in driving glasses.

First claim

The invention claimed is:

1. Photochromic polyfused naphthopyrans having the formulae (I), (II) and (III):

in which the R 1 , R 2 , R 3 , R 4 , R 7 , R 8 and R 10 radicals each independently represent a substituent selected from the group α consisting of a hydrogen atom, a (C 1 -C 18 )-alkyl radical, a (C 3 -C 7 )-cycloalkyl radical that may have one or more heteroatoms, a (C 1 -C 18 )-thioalkyl radical, a (C 1 -C 18 )-alkoxy radical, a hydroxyl group, a trifluoromethyl group, bromine, chlorine, fluorine, an un-, mono- or disubstituted phenyl, phenoxy, benzyl, benzyloxy, naphthyl or naphthoxy radical, where these substituents may in turn be selected from the group β consisting of a hydrogen atom, a (C 1 -C 6 )-alkyl radical, a (C 3 -C 7 )-Cycloalkyl radical, a (C 1 -C 6 )-thioalkyl radical, a (C 1 -C 6 )-alkoxy radical, a phenyl radical, a benzyl radical or a naphthyl radical;
n represents an integer from 1 to 4;
or the R 1 and R 2 radicals together with the carbon atom bonded to these radicals form a three- to eight-membered carbo- or heteromonocyclic ring which optionally bears one or more substituents from group β, and to which one to three aromatic or heteroaromatic ring systems may be fused, where the ring system(s) is/are independently selected from benzene, naphthalene, phenanthrene, pyridine, quinoline, furan, thiophene, pyrrole, benzofuran, benzothiophene, indole and carbazole, which may in turn be substituted by one or more substituents selected from group β;
or two adjacent R 4 radicals form a fused benzene ring which may be un-, mono- or disubstituted, where the substituents may be selected from group β;
or two adjacent R 4 radicals form a 1,1-dimethylindene or benzofuran ring system fused via the double bond in the five-membered ring;
or two adjacent R 4 radicals form a 2H-chromene or 1H-isochromene ring system via the double bond in the heterocyclic six-membered ring,
the R 5 and R 6 radicals each independently represent a substituent selected from hydrogen, a (C 1 -C 18 )-alkyl radical, a phenyl radical, a benzyl radical or a naphthyl radical;
m represents an integer from 1 to 4;
or two adjacent —CR 5 R 6 — moieties form a fused benzene ring which may be un-, mono- or disubstituted, where the substituents may be selected from group β;
the R 9 radical represents a substituent selected from hydrogen, a (C 1 -C 18 )-alkyl radical, a phenyl radical, a benzyl radical or a naphthyl radical;
X′ in the formula (I) is selected from —SO 2 —, —CH 2 —, —C(CH 3 ) 2 —, —C(C 2 H 5 ) 2 —, —C(C 6 H 5 ) 2 —, —O—CH 2 —, —CH 2 —O—, —CH 2 —CH 2 —, —C(CH 3 ) 2 —CH 2 — or —CH 2 —C(CH 3 ) 2 —;
X in the formula (II) or (III) is selected from —O—, —S—, —SO 2 —, —N(C 1 -C 6 )-alkyl-, —NC 6 H 5 —, —CH 2 —, —C(CH 3 ) 2 —, —C(C 2 H 5 ) 2 —, —C(C 6 H 5 ) 2 —, —O—CH 2 —, —CH 2 —O—, —O—(C═O)—, —(C═O)—O—, —CH 2 —CH 2 —, —C(CH 3 ) 2 —CH 2 — or —CH 2 —C(CH 3 ) 2 —;
Y and Z are independently selected from —O—, —S—, —SO 2 —, —N(C 1 -C 6 )-alkyl-, —NC 6 H 5 —, —CH 2 —, —C(CH 3 ) 2 —, —C(C 2 H 5 ) 2 — or —C(C 6 H 5 ) 2 —, where Y or Z, optionally together with the respectively adjacent CR 5 R 6 moiety, may form a fused benzene ring which may be un-, mono- or disubstituted, where the substituents may in turn be selected from group β, or Y or Z together with the respectively adjacent CR 5 R 6 moiety form a fused naphthalene, 9,9-dimethylfluorene or dibenzofuran ring system which may in turn be substituted by one or more substituents selected from group β;
and in which B and B′ are independently selected from one of the following groups a) and b), where
a) is a mono-, di- or trisubstituted aryl radical, where the aryl radical is phenyl, naphthyl or phenanthryl, and
b) is an un-, mono- or disubstituted heteroaryl radical, where the heteroaryl radical is selected from pyridyl, furanyl, thienyl, benzofuranyl, benzothienyl, 1,2,3,4-tetrahydrocarbazolyl or julolidinyl;
where the substituents of the aryl and heteroaryl radicals in a) and b) are selected from group β or the —(O—CHR 13 —CH 2 ) q —OR 14 moiety where R 13 represents hydrogen or a methyl radical, R 14 represents hydrogen or a (C 1 -C 6 )-alkyl radical and q represents an integer from 1 to 50;
or the substituents in a) and b) are selected from group x consisting of amino, mono-(C 1 -C 18 )-alkylamino, di-(C 1 -C 18 )-alkylamino, phenethenyl un-, mono- or disubstituted on the phenyl ring, un-, mono- or disubstituted (phenylimino)methylene, un-, mono- or disubstituted (phenylmethylene)imino and un-, mono- or disubstituted mono- and diphenylamino, piperidinyl, 3,5-dimethylpiperidinyl, N-substituted piperazinyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, indolinyl, morpholinyl, 2,6-dimethylmorpholinyl, thiomorpholinyl, azacycloheptyl, azacyclooctyl, un-, mono- or disubstituted phenothiazinyl, un-, mono- or disubstituted phenoxazinyl, un-, mono-, di- or trisubstituted 9,10-dihydroacridinyl, un-, mono- or disubstituted 1,2,3,4-tetrahydroquinolinyl, un-, mono- or disubstituted 2,3-dihydro-1,4-benzoxazinyl, un-, mono- or disubstituted 1,2,3,4-tetrahydroisoquinolinyl, un-, mono- or disubstituted phenazinyl, un-, mono- or disubstituted carbazolyl, un-, mono- or disubstituted 1,2,3,4-tetrahydrocarbazolyl and un-, mono- or disubstituted 10,11-dihydrodibenz[b,f]azepinyl, where the substituent(s) may in turn independently be selected from group β;
or two directly adjacent substituents of the aryl and heteroaryl radicals in a) and b) constitute a V—(CR 11 R 12 ) p —W moiety where p represents an integer from 1 to 3, the R 11 and R 12 radicals each independently represent a substituent selected from β, and V and W are independently selected from —O—, —S—, —N(C 1 -C 6 )-alkyl-, —NC 6 H 5 —, —CH 2 —, —C(CH 3 ) 2 —, —C(C 2 H 5 ) 2 — or —C(C 6 H 5 ) 2 —;
or two or more adjacent CR 11 R 12 moieties are part of a fused benzene ring which may be un-, mono- or disubstituted, where the substituents may in turn be selected from group β;
or V and/or W together with the respectively adjacent CR 11 R 12 moiety form a fused benzene ring which may be un-, mono- or disubstituted, where the substituents may in turn be selected from group β.

2. Photochromic polyfused naphthopyrans as claimed in claim 1 , where the R 1 , R 2 , R 3 , R 4 , R 7 , R 8 and R 10 radicals are each independently selected from a hydrogen atom, a (C 1 -C 6 )-alkyl radical or a (C 3 -C 7 )-cycloalkyl radical.

3. Photochromic polyfused naphthopyrans as claimed in claim 1 , where X′ in the formula (I) is selected from —CH 2 —, —C(CH 3 ) 2 —, —C(C 2 H 5 ) 2 —, —C(C 6 H 5 ) 2 —, —O—CH 2 — or —CH 2 —O—.

4. Photochromic polyfused naphthopyrans as claimed in claim 1 , where X in the formula (II) or (III) is selected from —O—, —S—, —CH 2 —, —C(CH 3 ) 2 —, —C(C 2 H 5 ) 2 —, —C(C 6 H 5 ) 2 —, —O—CH 2 —, —CH 2 —O—, —CH 2 —CH 2 —, —C(CH 3 ) 2 —CH 2 — or —CH 2 —C(CH 3 ) 2 —.

5. Photochromic polyfused naphthopyrans as claimed in claim 1 , where Y and Z are independently selected from —O—, —CH 2 —, —C(CH 3 ) 2 —, —C(C 2 H 5 ) 2 — or —C(C 6 H 5 ) 2 —, where Y or Z, optionally together with the respectively adjacent CR 5 R 6 moiety, may form a fused benzene ring which may be un-, mono- or disubstituted, where the substituents may in turn be selected from group β.

6. Photochromic polyfused naphthopyrans as claimed in claim 1 , where the R 9 radical is a (C 1 -C 18 )-alkyl radical, a phenyl radical or a benzyl radical.

7. Photochromic polyfused naphthopyrans as claimed in claim 1 , where the B and B′ radicals are independently sel

Assignees

• Rodenstock Gmbh

Inventors

• Weigand Udo
• Zinner Herbert

Classifications

• C07D493/04

  Ortho-condensed systems · CPC title

• C09B57/00 Primary

  Other synthetic dyes of known constitution · CPC title

• G02B1/041

  Lenses · CPC title

• C07D495/04

  Ortho-condensed systems · CPC title

• G02B5/23

  Photochromic filters · CPC title