Indolinospiropyran compounds and methods for their manufacture

Details Indolinospiropyran compounds and methods for their manufacture Indolinospiropyran compounds and methods for their manufacture

2000-05-31

2003-02-18

Celsa, Bennett (Department: 1627)

Organic compounds -- part of the class 532-570 series

Organic compounds

Chalcogen in the nitrogen containing substituent

C252S586000, C252S588000, C351S044000, C430S345000

Reexamination Certificate

active

06521753

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to spiropyran compounds. In particular, the invention provides indolinospiropyran compounds and methods for their manufacture, which compounds are useful as photochromic compounds.
BACKGROUND OF THE INVENTION
Various classes of photochromic compounds have been synthesized and suggested for use in applications in which reversible color changes or darkening is induced by sunlight. For example, spiro(indolino)naphthopyrans and spiro(indolino)quinopyrans are described in GB Patent 2,174,711. Spiropyrans also are described in Brown, Glenn H. ed.,
Photochromism
(New York, 1971) and Durr, Heinz and Henri Bouas-Laurent eds.,
Photochromism
(Elsevier, 1990).
Spiropyran derivatives may be the best known organic compounds showing photochromism phenomenon, but the structures of reported spiropyrans are considerably limited. Thus, a need exists both for spiropyran compounds allowing further facile modifications as well as methods for the synthesis of diverse spiropyran compounds.
DESCRIPTION OF THE INVENTION AND ITS PREFERRED EMBODIMENTS
The present invention provides indolinospiropyran compounds, and particularly photochromic indolinospiropyran compounds, as well as methods for synthesizing these compounds. The indolinospiropyran compounds of the invention are substituted on the indole ring with succinimide, which substitution permits ring opening of the succinimide and modulation of the bulk and photochromic properties of the compounds.
In one embodiment, the invention provides a compound comprising, consisting essentially of, and consisting of the formula:
wherein R
1
is C
1
-C
18
alkyl, allyl, phenyl, mono- or disubstituted phenyl, phen(C
1
-C
4
)alkyl, or (C
1
-C
4
)alkoxycarbonyl (C
1
-C
4
)alkyl, R
2
and R
3
are each independently C
1
-C
4
alkyl, phenyl, mono- or di-substituted phenyl, benzyl, or combined to form a cyclic ring that is cyclohexyl, norbornyl or adamantyl ring, R
4
is hydrogen, hydroxy, trichloromethyl, trifluoromethyl, formyl, C
1
-C
4
alkyl, halogen, C
1
-C
4
alkoxy, nitro, cyano, C
1
-C
4
monohaloalkyl, C
1
-C
4
alkoxycarbonyl, or an aromatic sharing the two adjacent carbon atoms with the benzene portion of the pyran ring to form a condensed aromatic ring including, without limitation, naphthyl, phenanthrenyl, and quinolino, x equals 1, 2, or 3 provided that when x=1, R
4
may be located on any of the available carbon atoms of the benzene ring of the benzopyran moiety, preferably on the 6, 7, or 8 position and when x=2, each of the R
4
may be the same or different and located at the 6 and 8 or 5 and 7 positions, preferably at the 6 and 8 positions. R
1
preferably is a C
1
-C
4
alkyl, phenyl, benzyl, allyl, or ethoxycarbonyl ethyl, R
2
and R
3
preferably are each independently methyl, ethyl, or phenyl and R
4
preferably is C
1
-C
4
alkyl, C
1
-C
2
alkoxy, chloro, bromo, iodo, trifluoromethyl, or nitro.
In a preferred embodiment, the invention provides a compound comprising, consisting essentially of, and consisting of the formula:
wherein R
4
is hydrogen, hydroxy, trifluoromethyl, formyl, methyl, ethyl, methoxy, ethoxy, nitro, fluoro, chloro, bromo, or iodo, and x is 1 or 2.
Because the compounds of formulae I and II contain a succinimide portion, the properties of the compounds, such as solubility, sensitivity and the like, of the invention may be manipulated by ring opening of the succinimide using any of a variety of known methods. Suitable such methods are described, for example, in 48(12)
Heterocycles,
2677-2691 (1998).
Formulae I and II compounds may be prepared by any convenient known method and preferably are prepared using a solid phase organic synthesis. The use of solid phase synthesis is advantageous in that it provides ease in execution of the reaction, ease in product purification, and convenient handling of polar molecules throughout the synthetic protocol. Additionally, this approach permits use of commercially available starting materials and use of excess reactant to drive the reaction to completion and to surpass the side reactions. Key in the synthesis is the use of a polymer-supported indoline of the formula:
wherein R
1
, R
2
, and R
3
are the same as for formula (I). The solid support may be selected from any of a variety of hydroxy resins. Suitable hydroxy resins include, without limitation, hydroxymethyl polystyrene resin, Wang resin (also known as 4-hydroxymethyl phenoxy resin or “HMP resin”), HMPA-PEGA resin (or 4-hydroxymethylphenoxyacetic acid and bisacrylamidoprop-1-yl polyethyleneglycol), HMPB-BHA resin (or 4-hydroxy-3-methoxyphenoxybutyric acid benzhydrylamine), HMPB-MBHA resin (4-hydroxymethyl-3-methoxyphenoxybutyric acid-methylbenzhydrylamine), and combinations thereof The theoretical loading of the resin may be either low (e.g., less than about 0.1 mmole/g) or high (e.g., greater than about 0.4 mmole/g), but for production of greater quantities of product, preferably is high, more preferably about 0.4 to about 1.5 mmole/g. Either of about 100-200 mesh or about 200-400 mesh resin may be used. Preferred resins are an about 100-200 mesh high loading hydroxymethyl polystyrene or a Wang resin.
The solid support used will depend upon the reactants selected, the solvent used, and the product desired. The resin preferably has types and quantities of functional groups that permit efficient attachment of the reactants as well as efficient release of the product. Additionally, the resin must be swellable in the solvent used. The amount of resin used will depend on the amount of reactants used and the reaction scale desired. Generally, about 1 mg to about 100 g of resin may be used.
Formula III compounds, may be prepared by either of two reaction schemes using an aminoindoline compound of the following formula:
wherein R
1
, R
2
, and R
3
are as defined for formula I.
The reaction schemes for the preparation of the formula III compound using the aminoindolino compounds are as follows:
In Method A, an aminoindoline compound of formula IV is treated with succinic anhydride under conditions suitable to form succinamic acid. More specifically, the reaction is carried out at a temperature of about 0 to about 60° C., preferably about room temperature, under an inert atmosphere including, without limitation, argon or nitrogen, for about 3 to 24 hours. The amount of reactants used will depend on the amount of product desired and typically will be about 1 mg to about 100 g, preferably about 100 mg to about 10 g. A hydroxy resin along with diisopropyl carbodiimide (“DIC”) and dimethylamino pyridine (“DMAP”) then are added to the mixture to form a suspension bead. This suspension of bead is shaken under conditions suitable to carry out a coupling reaction. Suitable conditions for the reaction are a temperature of about 0 to about 60° C., preferably about room temperature, about 14 to 24 hours under an inert atmosphere. Progress of the coupling reaction may be monitored by any convenient means including, without limitation, FT-IR or single bead FT-IR. Typically, the reaction forming the indoline loaded resin is complete after 24 hours at room temperature.
In Method B, hydroxy resin is shaken with an excess of succinic anhydride under conditions suitable to carry out a coupling reaction. Suitable conditions for the reaction are a temperature of about 60 to 120° C., preferably about 70 to about 100° C., for about 10 to about 60 hours, preferably about 24 to about 48 hours. The progress of the reaction may be monitored by any convenient means and, generally, will be complete after 48 hours of refluxing. After completion of the reaction, excess succinic anhydride is washed away and the resin, now coupled with the succinic acid, is treated with an aminoindoline of formula IV along with 1-hydroxy benzotriazole (“HOBT”) and DIC. Conditions suitable for the treatment are a temperature of about 0 to 60° C., preferably room temperature, and an inert atmosphere.
In either method, loading typically is over about 95 percent. Any convenient method for testing loading may b

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