Red coloring hyperchromic 3H-naphtho[2,1-B]pyrans

Details Red coloring hyperchromic 3H-naphtho[2,1-B]pyrans Red coloring hyperchromic 3H-naphtho[2,1-B]pyrans

1999-12-16

2001-09-25

Tucker, Philip (Department: 1712)

Compositions

Light transmission modifying compositions

Displaying color change

C544S106000, C544S111000, C544S124000, C544S129000, C544S141000, C544S142000, C544S143000, C544S170000, C546S187000, C546S196000, C546S200000, C546S201000, C548S440000, C548S454000, C351S163000

Reexamination Certificate

active

06294112

ABSTRACT:

The present invention relates o novel red colouring, hyperchromic 3H-naphtho[2,1-b]pyran photochromes and articles containing them.
Photochromism is a well-known physical phenomenon and has been detailed in “Photochromism: Molecules and Systems” Studies in Organic Chemistry, 40, Eds. H. Dürr and H. Bouas-Laurent, Elsevier, 1990.
The 3H-naphtho[2,1-b]pyran system is known to be capable or exerting a photochromic effect as described for example by Y. Hirshberg and E. Fischer, J. Chem. Soc., 1954, 3129 and R. Livingstone et al., J. Chem. Soc., 1958, 2422.
The basic 3H-naphtho[2,1-b]pyran structure is illustrated below:
The 3H-naphtho[2,1-b]pyran system has been intensively studied, for example 3-spirocycloalkyl substituted 3H-naphtho[2,1-b]pyrans are described in U.S. Pat. No. 4,826,977 (1989), PCT WO 91/00861 (1991) and U.S. Pat. No. 5,532,361 (1996).
The photochromic properties of 3-alkyl or 3-cycloalkyl 3-aryl-3H-naphtho[2,1-b]pyrans have been described e.g. U.S. Pat. No. 4,818,096 (1989) and PCT WO 92/01959 (1992). However, 3,3-diaryl-3H-naphtho[2,1-b]pyrans have been shown to posses superior photochromic properties cf. the 3-spirocycloalkyl and 3-alkyl 3-aryl 3H-naphtho[2,1-b]pyrans, see for example PCT WO 97/06455 (1997) which describes 3-(4-biphenyl)-3-aryl-3H-naphtho[2,1b-]pyrans.
The type and position of substituents on the 3H-naphtho[2,1-b]pyran ring has been shown to be critical in controlling the colour, intensity and speed of the photochromic effect. The following patents illustrate such features: PCT WO 92/09593 (1992) describes 3,3-diaryl-3H-naphtho[2,1-b]pyrans which posses a substituent at the 5-position; PCT WO 95/00867 relates to 3,3-diaryl3H-naphtho[2,1-b]pyrans which contain an alkoxy or aryloxy substituent at the 8-position; U.S. Pat. No. 5,520,853 (1996) describes 3,3-diaryl-3H-naphtho[2,1-b]pyrans which contain an alkoxy or aryloxy function in the 6-position. Two closely related articles, PCT WO 94/22850 (1994) and U.S. Pat. No. 5,552,090 (1996), claim 3,3-diaryl-3H-naphtho[2,1-b]pyrans which have a cyclic amino function at the 6-position.
In addition to the effects of substituents located on the 3H-naphtho[2,1-b]pyrans ring, the presence of an ortho substituent on the 3-aryl function of 3,3-diaryl-3H-naphtho[2,1-b]pyran has been shown to influence the rate of bleaching of the photochromic effect, see U.S. Pat. No. 5,066,818 (1991) and PCT WO 95/00866 (1995).
We have now found that the presence of at least one 3(cyclic amino aryl) group imparts surprising and useful effects on the photochromism of 3H-naphtho[2,1-b]pyrans. In particular, this C-3 substituent not only provides photochromic materials with highly desirable rates of colouration and bleaching (fade) at ambient temperatures, but gives rise to materials which have a high induced optical density in the coloured form. Furthermore, by judicious choice of this C-3 group on the photochrome, the shade of the red colour which develops on irradiation can be fine tuned throughout the red region of the visible spectrum.
According to the present invention, there is provided a red-coloring photochromic naphtho[2,1-b]-pyran of the general formula (I)
wherein R
1
represents either H or a group of the formula —NR
2
R
3
or —OR
4
or SR
4
or R
7
, and wherein when R
1
is NR
2
R
3
, each of R
2
and R
3
, which may be the same or different, independently represents an alkyl group or a carobocyclic or heterocyclic group, or R
2
and R
3
taken together with the nitrogen atom to which they are attached represent a heterocyclic ring having one or more hetero atoms and which may be unsubstituted or carry at least one substituent selected from alkyl, aryl and heteroaryl groups; and wherein when R
1
is OR
4
or SR
4
, the substituent R
4
represents an alkyl group, a perhaloalkyl group or an aryl or heteroaryl group;
R
5
represents a saturated cyclic aminoaryl substituent selected from:
where the size of the saturated nitrogen-containing ring is from 3 to 30 atoms (inclusive of the N atom) and may incorporate one or more of the same or different heteroatoms or groups (X) where X is O, S, NH, N-alkyl, N-aryl or N-heteroaryl; or
R
5
represents an indolinoaryl substituent of formula
wherein R
10
and R
11
can, in addition to those functions specified below, be conjoined to form a ring of 5 to 8 atoms (including those which comprise the indoline ring), said ring being carbocyclic or heterocyclic where one or more of the ring carbon atoms is replaced by one or more of the same or different heteroatoms selected from O, S, or N, said nitrogen atom having either an H, alkyl, aryl or heteroaryl substituent; or R
5
may be of formula (II)
in which both m and n are integers between 2 and 5 and may be the same or different; or
R
5
represents an unsaturated cyclic aminoaryl substituent selected from:
and wherein R
6
may be the same as or different from R
5
, and when R
6
is different from R
5
it is selected from aryl, naphthyl and heteroaryl groups; and wherein R
7
, R
8
, R
9
, R
10
and R
11
of which there may be multiples of either the same or different, may be selected from hydrogen, alkyl, haloalkyl, alkythio, aryl, arylthio, heteroaryl, halogen, nitrile, carboxylate, ester, nitro in additon to those substituents specified for R
1
, or R
7
may represent a or heterocyclic ring fused to faces f, gh, i, j or k.
The photochromic properties exhibited by the novel pyran compounds of the present invention, namely those of a desirable rate of bleaching of the coloured form at ambient temperatures, a nigh induced optical density of the coloured form and control of the shade of red colour, render these compounds particularly useful as photochromic materials for incorporation into polymeric host materials so as to impart photochromic properties to the said polymeric host materials. Examples of applications of the polymeric host materials containing photochromic materials of the present invention include the manufacture of lenses for sunglasses and ophthalmic lenses, optical filters and windows for vehicles such as cars (including sunroofs), aircraft and ships and architectural uses e.g. windows for homes and for photochromic ‘stained glass’ windows. Additional uses may include incorporation into paints, inks and other like formulations.
The photochromic pyrans of the present invention may be incorporated into the ‘plastic’ host material by well established protocols for example as described in European patent no. 0254020 or U.S. Pat. No. 5,066,818.
The high induced optical density of the photochromic compounds of the present invention enables the amount of the photochromic materials required so as to impart a useful degree of photochromism to a polymeric host material or to a solution to be greatly reduced, thereby enabling a considerable saving of synthetic effort and cost. Furthermore, the use of reduced quantities of the photochromic materials of the present invention has the bonus that there is a consequent reduction in any undersirable colour that the photochromic materials may impart in the bleached state, either by way of inherent colour of the material itself or by the formation of coloured fatigue/degradation products through use of the photochromic material.
Typical host materials are polymer materials, preferably optically clear materials, such as polymers of polyol (allyl carbonate)-monomers, polyacrylates such as polymethylmethacrylates, cellulose acetate cellulose triacetate, cellulose acetate propionate cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), polyurethanes, polycarbonate, polyethylene terephthalate, polystyrene, poly(triethyleneglycol dimethylacrylate), poly(diethyleneglycol bis(allyl carbonate)) and various copolymer mixes.
The naphtho[2,1-b]pyrans of the present invention may be prepared by a general method which is based on the following, reaction scheme:
This general synthetic methodol

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