3H-naphtho [2,1-B] pyrans as photochromic dichroic dyes and optical article containing them

Patent metadata

Field	Value
Publication number	US-9249136-B2
Application number	US-43973809-A
Country	US
Kind code	B2
Filing date	Sep 6, 2006
Priority date	Sep 6, 2006
Publication date	Feb 2, 2016
Grant date	Feb 2, 2016

Abstract

A naphthopyran compound represented by the formula (I):

wherein:
n 1 , n 2 , p, q is an integer comprised from 0 to 5 inclusive; m is an integer comprised from 0 to 4 inclusive; R 1 and R 2 represent a group selected from halogen, —R a , —OH, —OR a , —SH, —SR a , —NH 2 , —NR a R a1 , —NR b R c , —CO—R a , and —CO 2 R a1 , wherein R a , R a1 , R b and R c , are as defined in the description; R 3 represents a group selected from halogen, —R a , —OH, —OR a , —SH, —SR a , —NH 2 , and —NR a R a1 ; R 4 represents a group selected from halogen, —R a , —OH, —OR a , —SH, —SR a , —NH 2 , —NR a R a1 , —CO—R a , and —CO 2 R a1 ; R 5 represents a group selected from:
halogen, —R a , —OH, —OR a , —SH, —SR a , —NH 2 , and —NR a R a1 , wherein R a and R a1 are as defined hereinbefore, or when q is equal to 2, then two R 5 together represent further a group —O—(CH 2 ) q1 —O— wherein q1 represents an integer comprised from 1 to 3 inclusive.

First claim

The invention claimed is:

1. A naphthopyran compound represented by the formula (I):

wherein:
n 1 is an integer comprised from 0 to 5 inclusive;
n 2 is an integer comprised from 0 to 5 inclusive;
p is an integer comprised from 0 to 5 inclusive;
m is an integer comprised from 0 to 4 inclusive;
q is an integer comprised from 0 to 5 inclusive;
R 1 and R 2 , identical or different, independently from each other, a group halogen, —R a , —OH, —OR a , —SH, —NH 2 , —NR a R a1 , —NR b R c , —CO—R a , —O—CO—R a and —CO 2 R a1 , wherein:
R a is a linear or branched (C 1 -C 18 ) alkyl group or a linear or branched (C 1 -C 18 ) perfluoroalkyl group;
R a1 is a hydrogen, linear or branched (C 1 -C 18 ) alkyl group and linear or branched (C 1 -C 18 ) perfluoroalkyl group;
wherein R b and R c ,
together and in combination with the nitrogen atom, represent a saturated 5 to 7 membered heterocyclic group which comprises optionally one additional heteroatom selected from O, N or S, and which may be optionally substituted by a halogen, R a , —OH, —OR a , —NH 2 , or —NR a R a1 , wherein R a and R a1 are as defined hereinbefore;
or together and in combination with the nitrogen atom and the adjacent phenyl group form a heterocyclic group of formula (A):

R 3 is a halogen, —R a , —OH, —OR a , —SH, —SR a , —NH 2 , and NR a R a1 , wherein R a and R a1 are as defined hereinbefore;
R 4 is a halogen, —R a , —OH, —OR a , —SH, —SR a , —NH 2 , —NR a R a1 , —CO—R a , or —CO 2 R a1 , located at the para-position of the phenyl group, wherein R a and R a1 are as defined hereinbefore;
R 5 is;
a halogen, —R a , —OH, —OR a , —SH, —SR a , —NH 2 , or —NR a R a1 , wherein R a and R a1 are as defined hereinbefore,
or when q is equal to 2 and then two R 5 substituents are located onto two adjacent carbon atoms selected from C-7, C-8, C-9 and C-10 of the naphtho[2,1-b]pyran group, they may further represent together a group —O—(CH 2 ) q1 —O— wherein q1 represents an integer comprised from 1 to 3 inclusive.

2. The naphthopyran compound according to claim 1 , wherein:
n 1 is equal to 0 or 1, and R 1 is a halogen, —OH or —OR a located at the para- or ortho-position of the phenyl group;
n 2 is equal to 1 and R 2 is a halogen, —OH, —OR a , or —NR b R c located at the para-position of the phenyl group, wherein R a , R b and R c are as defined hereinbefore;
m is equal to zero;
p is equal to 1 and R 4 is —R a , —OR a , or —NR a R a1 ; and
q is an integer comprised from 0 to 2 inclusive, and R 5 is —OH or —OR a located on the C-8 and/or C-9 of the naphtho[2,1-b]-pyran group.

3. The naphthopyran compound of claim 1 , which is selected from one of the following compounds:
6-(4-Pentyl-4-biphenyl)-3-phenyl-3-(4-piperidinophenyl)-3H-naphtho[2,1-b]pyran;
6-(4-Pentyl-4-biphenyl)-3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-3H-naphtho[2,1-b]pyran;
6-(4-Pentyl-4-biphenyl)-3-phenyl-3-(4-pyrrolidinophenyl)-3H-naphtho[2,1-b]pyran;
6-(4-Pentyl-4-biphenyl)-3-phenyl-3-(julolidin-9-yl)-3H-naphtho[2,1-b]pyran;
6-(4-Pentyl-4-biphenyl)-3-(4-methoxyphenyl)1-3-(julolidin-9-yl)-3H-naphtho[2,1-b]pyran;
6-(4-Pentyl-4-biphenyl)-3-phenyl-3-(4-fluorophenyl)-3H-naphtho[2,1-b]pyran;
6-(4-Butoxy-4-biphenyl)-3-phenyl-3-(4-pyrrolidinophenyl)-3H-naphtho[2,1-b]pyran;
6-(4-Hexyloxy-4-biphenyl)-3-phenyl-3-(4-pyrrolidinophenyl)-3H-naphtho[2,1-b]pyran;
6-(4-Hexyloxy-4-biphenyl)-3-(4-fluorophenyl)-3-(4-pyrrolidinophenyl)-3H-naphtho[2,1-b]pyran;
6-(4-Pentyl-4-biphenyl)-3-(4-fluorophenyl)-3-(4-pyrrolidinophenyl)-3H-naphtho[2,1-b]pyran;
6-(4-Hexyloxy-4-biphenyl)-8,9-dimethoxy-3-phenyl-3-(4-piperidinophenyl)-3H-naphtho[2,1-b]pyran;
6-(4′-(Dibutylamino)-4-biphenyl)-8,9-dimethoxy-3-phenyl-3-(4-pyrrolidinophenyl)-3H-naphtho[2,1-b]pyran;
6-(4-Hexyloxy-4-biphenyl)-8,9-dimethoxy-3-phenyl-3-(4-pyrrolidinophenyl)-3H-naphtho[2,1-b]pyran;
3-(4-Butoxyphenyl)-8,9-dimethoxy-6-(4′-hexyloxy-4-biphenyl)-3-(9-julolidinyl)-3H-naphtho[2,1-b]pyran;
8,9-Dimethoxy-6-(4′-dodecyloxy)-4-biphenyl)-3-phenyl-3-(4-pyrrolidinophenyl)-3H-naphtho[2,1-b]pyran; and
8,9-Dimethoxy-6-(4′-dodecyloxy-4-biphenyl)-3-(4-hexyloxyphenyl)-3-[4-(4-methylpiperidino)phenyl]-3H-naphtho[2,1-b]pyran.

4. An optical article comprising at least one naphthopyran compound according to claim 1 .

5. The optical article according to claim 4 , wherein the article further comprises a polymeric host material, the at least one naphthopyran compound being incorporated in the bulk of said polymeric host material.

6. The optical article according to claim 5 , wherein the polymeric host material is selected from polymers of polyol(allyl carbonate) monomers, polyacrylates, poly(triethyleneglycol dimethacrylate), polyperfluoroacrylates, cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), polyurethanes, polycarbonates, poly(ethylene terephthalate), polystyrene), polyfluorostyrene, poly(diethylene glycol bis(alkyl carbonate)) or mixtures thereof.

7. The optical article according to claim 4 , wherein the article comprises an optical substrate and at least one film or coating comprising the at least one naphthopyran compound.

8. The optical article according to claim 7 , wherein the at least one film or coating is a dichroic film or coating comprising an anisotropic oriented polymer layer and the at least one naphthopyran compound.

9. The optical article according to claim 4 , wherein the article further comprises a host medium selected from a fluid host medium, a mesomorphous host medium, a gel host medium, or a mixture of a fluid, mesomorphous or gel host medium, wherein the at least one naphthopyran compound is dissolved or dispersed within the host medium.

10. The optical article according to claim 9 , wherein the host medium incorporating the at least one naphthopyran compound is selected from the group consisting of organic solvents, liquid crystals, liquid crystal polymers and mixtures thereof.

11. The optical article according to claim 9 , wherein the article comprises a device that includes a mechanism for holding the host medium incorporating the at least one naphthopyran compound in a mechanically stable environment.

12. The optical article according to claim 11 , wherein the device comprises a pair of opposed substrates having a gap there between for receiving the host medium and the at least one photochromic dye, and a frame for holding said pair of substrates adjacent one another.

13. The optical article according to claim 11 , wherein the device comprises an optical component provided with at least one transparent cell arrangement juxtaposed in a parallel direction to the surface thereof, each cell being tightly closed and containing said host medium and said at least one naphthopyran compound.

14. The optical article according to claim 13 , wherein the transparent cell arrangement forms a layer whose height perpendicular to the optical component surface is less than 100 μm.

15. The optical article according to claim 13 , wherein the optical component comprises a transparent rigid substrate on which the transparent cell arrangement is formed.

16. The optical article according to claim 13 , wherein the optical component comprises a transparent rigid substrate and, applied on said substrate, a transparent film incorporating the transparent cell arrangem

Assignees

• Aiken Stuart
• Cano Jean-Paul
• Gabbutt Christopher David
• Heron Bernard Mark
• Kosa Tamas
• Su Linli
• Sukhomlinova Ludmila
• Taheri Bahman
• Essilor Int
• Alphamicron Inc

Inventors

• Aiken Stuart
• Cano Jean-Paul
• Gabbutt Christopher David
• Heron Bernard Mark
• Kosa Tamas
• Su Linli
• Sukhomlinova Ludmila
• Taheri Bahman

Classifications

• C07D405/10

  linked by a carbon chain containing aromatic rings · CPC title

• C07D471/04 Primary

  Ortho-condensed systems · CPC title

• C07D311/92

  Naphthopyrans; Hydrogenated naphthopyrans · CPC title

• C07D455/04

  containing a quinolizine ring system condensed with only one six-membered carbocyclic ring, e.g. julolidine · CPC title