Photochromic compounds

Details Photochromic compounds Photochromic compounds

2000-06-19

2001-10-16

Raymond, Richard L. (Department: 1624)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Processes of preparing a desired or intentional composition...

C544S071000, C524S090000

Reexamination Certificate

active

06303673

ABSTRACT:

The present invention relates to novel hyperchromic, rapid responding, photochromic spiroindolinonaphthoxazines which are of green or green-blue colouring, and to articles and compositions containing them.
Photochromism is a well established phenomenon and has been detailed in “Photochromism: Molecules and Systems,” Studies in Organic Chemistry, vol. 40, eds. H. Dürr and H. Bouas-Laurent, Elsevier, 1990. Much effort has been directed to exploring the photochromic properties of naphth[2,1-b][1,4]oxazines and many derivatives of this ring system are known. However, there are few examples of photochromic compounds based on the naphth[1,2-b][1,4]oxazine system to date, see for example Jpn. Kokai Tokkyo Koho JP 62 33,184 (1997 Chem. Abstr. 107, 187531) and Eur. Patent EP 0 449 669 A1 [1991]. These patents disclose compounds which possess the basic structural unit illustrated below and which show blue-purple photochromism upon irradiation:
1,3-dihydrospiro[2H-indole-2,2′-[2H]naphth[1,2-b][1,4]oxazine]
We have now devised a novel modification of the naphth[1,2-b][1,4]oxazine system which permits access to green or blue-green colouring photochromic dyes with excellent colourability, rapid photochromic response, high fatigue resistance and a favourable background colour. Moreover, by judicious choice of substituents greatly differing rates of bleaching can be achieved.
In one aspect, the invention provides a photochromic compound having the general formula (I):
wherein:
(a) —R
1
is selected from the following aminoaryl moieties:
in which R
7
and R
8
, which may be the same or different, are each selected from a linear or branched C
1
-C
20
alkyl group, an aryl group, a heteroaryl group, a linear or branched C
1
-C
20
alkylaryl group, a linear or branched C
1
-C
20
alkyl -cycloalkyl or -bicycloalkyl or -tricycloalkyl or substituted -cycloalkyl or -bicycloalkyl or -tricycloalkyl group, a linear or branched C
1
-C
20
haloalkyl or perhaloalkyl group, a linear or branched C
1
-C
20
alkoxyalkyl or peralkoxyalkyl group, a linear or branched C
1
-C
20
alkylthioalkyl or peralkylthioalkyl group, a linear or branched C
1
-C
20
aminoalkyl or peraminoalkyl group, a C
3
-C
20
cycloalkyl or substituted cycloalkyl group, a C
4
-C
20
bicycloalkyl or substituted bicycloalkyl group, a C
6
-C
20
tricycloalkyl or substituted tricycloalkyl group, a linear or branched C
1
-C
20
hydroxyalkyl or a perhydroxyalkyl group; or
(b) —R
1
is selected from cyclic aminoaryl moieties in which R
7
and R
8
are conjoined according to the following structures:
wherein the size of the nitrogen containing ring is from 3 to 40 atoms (inclusive of the N atom) and may incorporate one or more of the same or different groups of atoms (X) which may be arranged in any sequence and where X may be selected from CH
2
, CHR
7
, CR
7
R
8
, CHaryl, C(aryl)
2
, C(alkyl,aryl), O, S, S(O), S(O)
2
, NH, N-alkyl, N-aryl, P-alkyl, P-aryl, P(O)alkyl P(O)aryl, P(O)Oalkyl; wherein R
7
and R
8
may each be selected from those substituents specified above; or
(c) —R
1
may represent an N-indolinoaryl or N-tetrahydroquinolino aryl substituent of the structure:
wherein R
11
, R
12
and R
13
are each a C
1
-C
5
linear or branched alkyl group or aryl group, or any two groups selected from R
11
, R
12
and R
13
may be conjoined to form a ring of 5 to 8 atoms (including those of the indoline or tetrahydroquinoline ring); or
(d) —R
1
may be represented by the structure (II) below, in which the N-atom is incorporated at the bridgehead position in a tricyclic nitrogen heterocycle, and p and q are both integers between 2 and 6 and may be the same or different;
and wherein —R
3
is a linear or branched C
1
-C
20
alkyl group, a linear or branched C
2
-C
20
alkenyl or polyalkenyl group in any E or Z geometrical isomeric form, a C
2
-C
20
alkyl or polyalkynyl group, an aryl group, a heteroaryl group, a linear or branched C
1
-C
20
alkyl aryl group, a linear or branched C
1
-C
20
alkyl -cycloalkyl or -bicycloalkyl or -tricycloalkyl or substituted -cycloalkyl or -bicycloalkyl or -tricycloalkyl group, of which the following are non-limiting illustrative examples:
a linear or branched C
1
-C
20
haloalkyl or perhaloalkyl group, a linear or branched C
1
-C
20
alkoxyalkyl or peralkoxyalkyl group, a linear or branched C
1
-C
20
alkylthioalkyl or peralkylthioalkyl group, a linear or branched C
1
-C
20
aminoalkyl or peraminoalkyl group, a C
3
-C
20
cycloalkyl or substituted cycloalkyl group, of which the following are non-limiting illustrative examples:
a C
4
-C
20
bicycloalkyl or substituted bicycloalkyl group, of which the following are non-limiting illustrative examples:
a C
6
-C
20
tricycloalkyl or substituted tricycloalkyl group, such as for example:
or a linear or branched C
1
-C
20
hydroxyalkyl or perhydroxyalkyl group; and
wherein —R
4
and —R
5
, which may be the same or different, are each selected from the substituents specified for —R
3
above, or —R
4
and —R
5
may be conjoined to form a spiro linked C
3
-C
20
cyclic system or substituted cyclic system; and wherein —R
6
of which there may be none, one or more than one, and which may be the same or different are each selected from H, C
1
-C
20
linear or branched alkyl C
1
-C
20
linear or branched alkoxy, C
1
-C
20
linear or branched alkylthio, hydroxy, amino, C
1
-C
20
linear or branched alkylamino, C
1
-C
20
linear or branched dialkylamino, C
1
-C
20
linear or branched alkyl arylamino, diarylamino, arylamino, benxylamino, dibenzylamino, C
2
-C
20
linear or branched alkanoylamino, aroylamino and cyclic amino and wherein —R
2
, R
9
and R
10
of which there may be none, one or more than one, and which may be the same or different, are each selected from hydrogen, halogen, nitro, nitroso, amino, acetamido, C2-C10 N-alkylamido, alkoxycarbonyl, nitrile, carboxy, hydroxy, aryloxy, C1-C10 alkoxy, a heteroatom which is O or N or S or P which in turn can be bonded either singly or multiply to carbon, oxygen, sulfur or nitrogen, C1-C5 alkoxy or allylthio or aryl or aryloxy or to multiples thereof, non-limiting illustrative examples of which are:
P(O)(OEt)
2
, SO
3
H, SO
3
Et, SO
2
H, SO
2
Ph, SOMe, P(Ph)
2
, P(O)(Ph)
2
, N=N-aryl
or —R
2
, R
9
and R
10
may each be selected from those substituents specified for —R
3
.
The invention also provides a process for making a photochromic compound of the invention, which process includes the following step:
wherein R
1
, R
3
, R
4
and R
5
are as defined in claim
1
, or represent groups which can be replaced by, or modified to form, groups as defined respectively in claim
1
, and wherein in the above step the reactants and/or product may also include substituents R
2
and R
6
as defined in claim
1
, or such substituents are introduced subsequently. This is an expeditious and practicable synthesis of these materials.
The synthesis of naphthoquinone 2-oximes involves oximation of the readily available 4-aminoaryl-1,2-naphthoquinones, themselves accessible from 1,2-naphthoquinone or its 4-sulfonic acid salt. The methylene indoline derivative is readily available to those skilled in the art and the synthesis of these materials has been reviewed (see B. Robinson, “The Fischer Indole Synthesis,” Wiley, Chichester, 1982). Formation of the naphthoxazine is accomplished by heating the reactants in a solvent such as, for example, an alcohol, aromatic hydrocarbon or an ether.
The photochromic properties exhibited by the novel spironaphthoxazines of the present invention, namely those of a desirable rate of bleaching of the coloured form at ambient temperatures, a high induced optical density of the coloured form and control of the shade of green or blue-green colour, coupled with their excellent fatigue resistance, render these compounds particularly useful as photochromic materials for incorporation into polymeric host materials such as optical elements, for example, so as to impart photochromic properties

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