Photochromic annelated naphthopyrane systems with special substituents, for attaining rapid lightening speeds

Patent metadata

Field	Value
Publication number	US-11965102-B2
Application number	US-201917251445-A
Country	US
Kind code	B2
Filing date	Jun 5, 2019
Priority date	Jun 14, 2018
Publication date	Apr 23, 2024
Grant date	Apr 23, 2024

Abstract

The present invention relates to new photochromic, fused naphthopyran systems having specific substituents R 1 , which can be used to attain very rapid lightening speeds, without detriment to the depth of darkening after excitation, and also to the use thereof in plastics of all kinds.

First claim

The invention claimed is:

1. Photochromic fused naphthopyrans of the formula (II):

in which the radical R 1 , or R 1 and R 3 independently of one another, is/are the following moiety:

in which the radical R 13 is hydrogen or a methyl radical and the radical R 14 is a substituent selected from hydrogen, a (C 1 -C 6 )-alkyl radical, an acetyl radical, a benzoyl radical, a phenyl radical, a benzyl radical, a biphenylyl radical, a naphthyl radical, a tert-butyldimethylsilyl radical or a tert-butyldiphenylsilyl radical; n is an integer from 0 to 1, and p is an integer from 3 to 50; or, if R 13 is a methyl radical, R 14 may also be the moiety —(CH 2 —CH 2 ) q —OR 15 , in which case the radical R 15 may be selected from hydrogen, a (C 1 -C 6 )-alkyl radical, a phenyl radical, a benzyl radical or a biphenylyl radical, and q is an integer from 1 to 20; and
the radicals R 2 , R 3 and R 4 in each case independently of one another are a substituent selected from hydrogen, bromine, chlorine, fluorine, 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 18 )-alkoxy radical, a hydroxyl radical, a tert-butyldimethylsilyloxy radical, a tert-butyldiphenylsilyloxy radical, a trifluoromethyl radical, a phenyl radical, a 4-methoxyphenyl radical, a phenoxy radical, a 4-methoxyphenoxy radical, a benzyl radical, a 4-methoxybenzyl radical, a benzyloxy radical, a 4-methoxybenzyloxy radical, a biphenylyl radical, a diphenylyloxy radical, a naphthyl radical, a naphthoxy radical, a mono-(C 1 -C 6 )-alkylamino radical, a di-(C 1 -C 6 )-alkylamino radical, a phenylamino radical, a (C 1 -C 6 )-alkyl-phenylamino radical, a diphenylamino radical, a (4-methoxyphenyl)amino radical, a ((C 1 -C 6 )-alkyl)-(4-methoxyphenyl)amino radical, a bis(4-methoxyphenyl)amino radical, a piperidyl radical, a 3,5-dimethylpiperidyl radical, an indolinyl radical, a morpholinyl radical, a 2,6-dimethylmorpholinyl radical, a thiomorpholinyl radical, an azacycloheptyl radical, a phenothiazinyl radical, a phenoxazinyl radical, a 1,2,3,4-tetrahydroquinolyl radical, a 1,2,3,4-tetrahydroisoquinolyl radical, a phenazinyl radical, a carbazolyl radical, a 1,2,3,4-tetrahydrocarbazolyl radical or a 10,11-dihydrodibenz[b,f]azepinyl radical;
or the two adjacent radicals R 2 and R 3 are the moiety —V—(CH 2 ) r —W—, in which case V and W independently of one another are selected from the moieties —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 —; r is an integer from 1 to 3; with the proviso that if this numerical value is 2 or 3, there may also be a benzene ring fused to two adjacent CH 2 groups; V or W, together with the respectively adjacent CH 2 group, may also be a fused benzene ring;
or R 3 is the same moiety as R 1 ;
the radicals R 5 , R 8 , R 9 , R 10 , R 11 and R 12 each independently of one another are a substituent selected from hydrogen, a (C 1 -C 6 )-alkyl radical, a (C 3 -C 7 )-cycloalkyl radical, a phenyl radical, a benzyl radical, a biphenylyl radical or a naphthyl radical; where m is an integer from 1 to 3;
or two adjacent radicals R 5 form a fused benzene ring, which may be unsubstituted or mono- or disubstituted, in which case the substituents may be selected from hydrogen, a (C 1 -C 6 )-alkyl radical, a (C 1 -C 6 )-alkoxy radical, a phenyl radical, a benzyl radical, a biphenylyl radical or a naphthyl radical;
or two adjacent radicals R 5 form a fused benzofuran ring, a fused benzothiophene ring, a fused 2H-chromene ring, a fused 3,3-dimethylindene ring or a fused dioxane ring;
or the radicals R 8 and R 9 together form the moiety —(CH 2 ) s —, in which case s is an integer from 1 to 3; with the proviso that if this numerical value is 2 or 3, there may also be a benzene ring fused to two adjacent CH 2 groups.

2. Photochromic fused naphthopyrans as claimed in claim 1 , in which the radical R 1 represents the moiety:

and the radical R 3 is a substituent selected from hydrogen, bromine, chlorine, fluorine, 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 18 )-alkoxy radical, a hydroxyl radical, a tert-butyldimethylsilyloxy radical, a tert-butyldiphenylsilyloxy radical, a trifluoromethyl radical, a phenyl radical, a 4-methoxyphenyl radical, a phenoxy radical, a 4-methoxyphenoxy radical, a benzyl radical, a 4-methoxybenzyl radical, a benzyloxy radical, a 4-methoxybenzyloxy radical, a biphenylyl radical, a diphenylyloxy radical, a naphthyl radical, a naphthoxy radical, a mono-(C 1 -C 6 )-alkylamino radical, a di-(C 1 -C 6 )-alkylamino radical, a phenylamino radical, a (C 1 -C 6 )-alkyl-phenylamino radical, a diphenylamino radical, a (4-methoxyphenyl)amino radical, a ((C 1 -C 6 )-alkyl)-(4-methoxyphenyl)amino radical, a bis(4-methoxyphenyl)amino radical, a piperidyl radical, a 3,5-dimethylpiperidyl radical, an indolinyl radical, a morpholinyl radical, a 2,6-dimethylmorpholinyl radical, a thiomorpholinyl radical, an azacycloheptyl radical, a phenothiazinyl radical, a phenoxazinyl radical, a 1,2,3,4-tetrahydroquinolyl radical, a 1,2,3,4-tetrahydroisoquinolyl radical, a phenazinyl radical, a carbazolyl radical, a 1,2,3,4-tetrahydrocarbazolyl radical or a 10,11-dihydrodibenz[b,f]azepinyl radical; and in which the other radicals are as defined above.

3. Photochromic fused naphthopyrans as claimed in claim 1 , in which the radicals R 5 , R 8 , R 9 , R 10 , R 11 and R 12 each independently of one another are a substituent selected from hydrogen, a (C 1 -C 6 )-alkyl radical, a (C 3 -C 7 )-cycloalkyl radical, a phenyl radical, a benzyl radical, a biphenylyl radical or a naphthyl radical; where m is an integer from 1 to 3.

4. Photochromic fused naphthopyrans as claimed in claim 1 , in which the radical R 1 represents the following moiety:

in which the radical R 13 is hydrogen or a methyl radical and the radical R 14 is a substituent selected from hydrogen, a (C 1 -C 6 )-alkyl radical, an acetyl radical, a benzoyl radical, a phenyl radical, a benzyl radical, a biphenylyl radical, a naphthyl radical, a tert-butyldimethylsilyl radical or a tert-butyldiphenylsilyl radical; n is an integer from 0 to 1, and p is an integer from 3 to 50; or, if R 13 is a methyl radical, R 14 may also be the moiety —(CH 2 —CH 2 ) q —OR 15 , in which case the radical R 15 may be selected from hydrogen, a (C 1 -C 6 )-alkyl radical, a phenyl radical, a benzyl radical or a biphenylyl radical, and q is an integer from 1 to 20; and
the radical R 3 is a substituent selected from hydrogen, bromine, chlorine, fluorine, 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 18 )-alkoxy radical, a hydroxyl radical, a tert-butyldimethylsilyloxy radical, a tert-butyldiphenylsilyloxy radical, a trifluoromethyl radical, a phenyl radical, a 4-methoxyphenyl radical, a phenoxy radical, a 4-methoxyphenoxy radical, a benzyl radical, a 4-methoxybenzyl radical, a benzyloxy radical, a 4-methoxybenzyloxy radical, a biphenylyl radical, a diphenylyloxy radical, a naphthyl radical, a naphthoxy radical, a mono-(C 1 -C 6 )-alkylamino radical, a di-(C 1 -C 6 )-alkylamino radical, a phenylamino radical, a (C 1 -C 6 )-alkyl-phenylamino radical, a diphenylamino radical, a (4-methoxyphenyl)amino radical, a ((C 1 -C 6 )-alkyl)-(4-methoxy

Assignees

• Rodenstock Gmbh

Inventors

• Weigand Udo
• Zinner Herbert
• Rohlfing Yven

Classifications

• C09B69/109 Primary

  containing other specific dyes · CPC title

• C09K9/02

  Organic tenebrescent materials · CPC title

• C09K2211/1018

  Heterocyclic compounds · CPC title

• G02C7/102

  Photochromic filters · CPC title

• C07D311/92 Primary

  Naphthopyrans; Hydrogenated naphthopyrans · CPC title