CA2219450A1 - Novel pre-dyes - Google Patents
Novel pre-dyes Download PDFInfo
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- CA2219450A1 CA2219450A1 CA002219450A CA2219450A CA2219450A1 CA 2219450 A1 CA2219450 A1 CA 2219450A1 CA 002219450 A CA002219450 A CA 002219450A CA 2219450 A CA2219450 A CA 2219450A CA 2219450 A1 CA2219450 A1 CA 2219450A1
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- dye
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
- G03C1/732—Leuco dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0077—Preparations with possibly reduced vat, sulfur or indigo dyes
Abstract
One embodiment of the present invention is a method and compositin comprising a novel pre-dye molecule that is colorless and stable to ordinary light. The pre-dye molecule is capable of forming a color when exposed to certain wavelengths of electromagnetic radiation. A second embodiment of the present invention is a method of converting a conventional leuco dye to a colored composition by exposing the leuco dye admixed with a radiation transorber to certain wavelengths of electromagnetic radiation.
Description
CA 022194~0 1997-11-17 WO 96t39646 PCT/US9C~'u33.3 7 NOVEL PRE-DYES
Cross-Reference to Related Applications This application is a continuation-in-part application of U.S.
Serial No. 08/649,754, filed May 29, 1996, which is a continuation-in-part application of U.S. Serial No. 08/463,187, filed on June ~, 1995, which are all hereby incorporated by l~r~rt;llce.
Technical Field The present invention relates to novel pre-dyes that are colorless and develop color when exposed to certain wavelengths of electrom~gnstic radiation. The present invention also relates to methods of changing conventional leuco dyes to form colored compositions when exposed to certain wavelengths of electromagnetic radiation.
Background of the Invention It is well known that dyes, in their reduced leuco ~orm, can provide the basis of color image forming systems. The leuco dyes may initially be relatively colorless, but can return to a colored form ' 30 when oxidized, e.g., by nitrate salts in the presence of heat.
Examples of leuco dyes used in color image forming systems include triarylmethanes, xanthenes, styryl dyes, and azine dyes, such as, for example, phen~7in~, phenoxazines, and phenothi~7ines.
It is also known that the leuco form of a given dye may suffer 3s from instability under ambient conditions and can often revert CA 022194~0 1997-11-17 spontaneously to the colored form of the dye. This tendency is increased when photoxidizing agents, for example, trihalogenomethyl compounds which split off halogen radicals upon exposure, are added to obtain an intencification of contrast. A number of stabilizers, for example, sulfur compounds, phenols and other reducing agents have therefore been recommPnt1ed for leuco dye compositions.
Thus, what is needed is a leuco dye that is stable in solution even in the presence of artificial light or sunlight. The ideal leuco dye would be converted to stable colored molecules by exposure to electromagnetic radiation that normally would not be present in ordinary light. In sllmm~ry, it would be extremely desirable to obtain stable leuco derivatives of dyes that could be transformed to a stable colored molecule.
Snmm~ry of the Invention One embodiment of the present invention is a method and composition comprising a novel pre-dye molecule that is colorless and stable to ordinary light. The pre-dye molecule is capable of forming a color when exposed to certain wavelengths of electrom~gnetic radiation.
In particular, the novel pre-dye of the present invention is a dye that is covalently attached to a radiation transorber. The resulting pre-dye molecule is stable in ordinary light but is mutable when exposed to the a~opliate wavelength of electromagnetic radiation. The radiation transorber is desirably composed of a wavelength-specific sensitizer and a photoreactor. When the pre-dye is exposed to the appropriate wavelength of electromagnetic radiation, the pre-dye molecule m~lt~tes and is transformed into the stable colored form of the dye. Accordingly, the present invention also encompasses a method of forming color by exposing the pre-dye to the a~rop.iate wavelength of ultraviolet radiation.
Another embo-lim~nt of the present invention is a conventional leuco dye that is admixed with a radiation transorber, preferably with a molecular includant. When the adllli~LuLe is exposed to the CA 022194~0 1997-11-17 WO 96/39646 PCT/US~6/0~7 ~ro~liate wavelength of electrom~gnPtic radiation, the leuco dye is converted to its colored form.
Yet another emborlim~-nt of the present invention is a method of converting a conventional leuco dye to a colored composition by exposing the leuco dye admixed with a radiation transorber to certain wavelengths of electrom~netic radiation The present invention can be used in im~ing processes including photoim~ing processes, security systems, printing processes, recording processes and the like.
These and other objects, features and advantages of the present invention will become apparent after a review of the following (let~ d description of the disclosed embodiments and the appended claims.
Detailed Description of the Invention The present invention relates, in one aspect, to pre-dyes that are mutable by exposure to narrow band-width radiation to form colored compounds. The present invention more particularly relates to a composition, the pre-dye, comprising a dye molecule which is covalently ~tt~.herl to a radiation transorber. When the dye molecule is covalently ~tt~rh~l to the radiation transorber, the composition is colorless. The pre-dye is mutable when exposed to specific, narrow band-width radiation and mllt~tes to the stable colored form of the dye. Accordingly, the present invention also encompasses a method 2s of forming color by exposing the pre-dye to the appropriate wavelength of ultraviolet radiation.
In another embodiment of the present invention, the composition of the present invention includes an admixture of a conventional leuco dye and a radiation transorber. The leuco dye, in the presence of the radiation transorber, is adapted, upon exposure of the transorber to radiation, preferably ultraviolet radiation, to be mutable to a colored composition. The preferred radiation transorber is adapted to absorb ultraviolet radiation and interact with the leuco dye to effect the irreversible mutation of the molecule to a 3s colored composition.
CA 022194~0 1997-11-17 WO 96/39646 PCI~/US96/08887 Yet another embo~limPnt of the present invention is a method of converting a conventional leuco dye to a colored composition by exposing the leuco dye a-lmixed with a radiation transorber to certain wavelengths of electrom~gnPtic radiation After definitions of various terms used herein, the pre-dye of the present invention and methods of developing color using the same are described in detail, followed by a description of the leuco dye/radiation transorber admixture and methods of developing color using the same.
Definitions As used herein, the term "dye" is meant to include, without limitation, any m~tPri~l which typically will be an organic rn~tçri~l, such as an organic colorant or pi~;mP~t Desirably, the dye will be substantially transparent to, that is, will not significantly interact with, the ultraviolet radiation to which it is exposed. The term is meant to include a single m~teri~l or a mixture of two or more m~teri~
The term "pre-dye" or "pre-dye molecule" as used herein m~n.~ a dye molecule that is covalently attached to a radiation transorber so that the composition is colorless. Upon irradiation with the appropriate wavelength of electromagnetic radiation, the composition is capable of ft~rming a colored composition.
The term "leuco dye" refers to the leuco form of a dye, or 2s colorless form, and is the reduced form of the dye having one or two hydrogen atoms, the removal of which, together with an additional electron in certain cases, produces the colored dye.
As used herein, the term "irreversible" means that the dye will not revert to its original color when it no longer is exposed to ultraviolet radiation.
The term "composition" and such variations as "colored composition" are used herein to mean a dye, and a radiation transorber. When reference is being made to a colored composition which is adapted for a specific application, the term "composition-CA 022194~0 1997-11-17 WO 96/39646 PCT/US96/0~87 based" is used as a modifier to indicate that the material includes a dye, a radiation transorber and, optionally, a molec~ r incl~ nt The term "molecular incl~ nt," as used herein, is intended to mean any substance having a chemical structure which ~lefinPs at least one cavity. That is, the molecular includant is a cavity-cont~inin~
structure. As used herein, the term "cavity" is meant to include any opening or space of a size sufficient to accept at least a portion of one or both of the dye and the radiation transorber. The molecular includant can also include a cavity-cont~inin~ molecule to which the radiation transorber is optionally covalently attached. A description of the method of preparing molecular includants covalently ~tt~'h~d to radiation transorbers, and their association with colorants, is described in Examples 6-24, and in copending patent application serial no. 08/461,372, filed June 5, 1995, which is incorporated herein by reference.
The term "functionalized molecular includant" is used herein to mean a molecular includant to which one or more molecules of an ultraviolet radiation transorber are covalently coupled to each molecule of the molecular includant. The term "degree of substitution" is used herein to refer to the number of these molecules or leaving groups (defined below) which are covalently coupled to each molecule of the molecular inch~ nt The term "derivatized molecular includant" is used herein to mean a molecular includant having more than two leaving groups covalently coupled to each molecule of molecular includant. The term "leaving group" is used herein to mean any leaving group capable of participating in a bimolecular nucleophilic substitution reaction.
The term "ultraviolet radiation" is used herein to mean electromagnetic radiation having wavelengths in the range of from about 4 to about 400 nanometers. The especially desirable ultraviolet radiation range for the present invention is between approximately 100 to 375 nanometers. Thus, the term includes the regions commonly referred to as ultraviolet and vacuum ultraviolet. The wavelength ranges typically assigned to these two regions are from CA 022194~0 1997-11-17 about 180 to about 400 nanometers and from about 100 to about 180 nanometers, respectively.
The term "mutable," with reference to the pre-dye or the leuco dye/radiation transorber mixture is used to mean that the absorption s maximum of the dye is capable of being mutated or changed by exposure to radiation, preferably ultraviolet radiation, when in the presence of the radiation transorber so that the absorption ma~iml-m is shifted to the visible region. In general, it is only necessary that such absorption maximllm be mllt~te~l to an absorption ma~imllm which is different from that of the pre-dye prior to exposure to the ultraviolet radiation, and that the mutation be irreversible. In other words, the dye can mllt~te from colorless to a color.
The term "compound" is intended to include a single m~teri~l or a ll~ib~Lule of two or more materials. If two or more m~teri~l.c OEe lS employed, it is not nPcess~ry that all of them absorb radiation of the same wavelength. As discussed more fully below, a radiation transorber is comprised of a photoreactor and a wavelength selective sen~iti7f~r~
The term "radiation transorber" is used herein to mean any m~teri~l which is adapted to absorb radiation at a specific wavelength and interact with the dye to affect the mllt~tion of the dye. In some embo-l;meIlts, the radiation transorber may be an organic compound.
A description of the synthesis of the radiation transorber is described in Examples 6-8, and 13, and in copending patent application serial 2s no. 08/461,372, filed June 5, l99S, which is incorporated herein by reference.
Pre-Dye Molecule One embodiment of the present invention is a pre-dye molecule that is mutable by exposure to narrow band-width radiation to form a colored compounds. The present invention more particularly relates to a composition, the pre-dye molecule or "pre-dye", comprising a dye molecule which is covalently attached to a radiation transorber. When the dye molecule is covalently attached 3s to the radiation transorber, the composition is colorless. The pre-CA 022194~0 1997-11-17 dye is mutable when exposed to specific, narrow band-width radiation and mutates to the stable colored form of the dye.
The present invention includes unique compounds, namely, radiation transorbers, that are capable of absorbing narrow wavelength ultraviolet radiation. The compounds are synthesized by combining a wavelength-selective sensitizer and a photoreactor.
Generally, photoreactors do not efficiently absorb high energy radiation. However, when a photoreactor is combined with a wavelength-selective sensitizer, the resulting compound is a wavelength specific compound that efficiently absorbs a very narrow spectrum of radiation. In this compound the wavelength-specific sensitizer generally absorbs radiation having a specific wavelength, and therefore a specific amount of energy, and transfers the energy to the photoreactor. Desirably, the wavelength-selective sensitizer is covalently coupled to the photoreactor.
Accor~ngly, th~ radiati~n transorber that is attached to the dye molecule is capable of absorbing radiation and interacting with the dye molecule to effect a mllt~tion of the pre-dye to form a colored compound. The radiation transorber may be any material which is adapted to absorb radiation and interact with the dye to effect the mutation of the dye. It is desirable that the mutation of the pre-dye be irreversible. In the desired embodiment, the radiation transorber is covalently attached to the dye molecule thereby rendering the dye molecule colorless.
By way of example, the wavelength-selective sensitizer may be, but is not limited to, phthaloylglycine or 4-(4-hydroxy-phenyl)-2-butanone. These wavelength-specific sensitizers are illustrated below:
Phthaloylglycine [~N {~H2--C--OH
~ = = ~
CA 022194~0 1997-11-17 WO 96/39646 PCT/US9CI~ 9~7 4-(4-Hydroxy phenyl) butan-2-one CH3--C--CH2~H2~30H
The photoreactor may be, but is not limited to, 1-(4-(2-hydroxyethoxy)phenyl)-2-hydroxy-2-methylpropan-1-one (Darocur-2959) or l-hydroxycyclohexane phenyl ketone (Irgacure 184).
These reactive species-generating photoinitiators are illustrated below:
HO--(CH2)2--~~ CH
Irgacure 184 (l-hydroxycyclohexane phenyl ketone) C~OHJ~
It is to be understood that the above n~m~l sensitizers and photoreactors are named in their unbonded form. For example, where the photoreactor l-hydroxycyclohexane phenyl ketone is covalently bonded to a sensitizer via its hydroxy group, the photoreactor moiety may be denoted as cyclohexyl-phenyl ketone ester. Where the sensitizer 4-(4-hydroxyphenyl)-2-butanone is 2s covalently bonded to a photoreactor via its hydroxy group, the sensitizer moiety may be denoted as 4-(4-oxyphenyl)-2-butanone.
Similarly, where the sensitizer phthaloylglycine is covalently bonded to a photoreactor via its hydroxy group, the sensitizer moiety may be denoted as phthaloylglycyl. When the sensitizer is covalently bonded to the photoreactor, these sensitizers and photoreactors may be ref~lled to in their unbonded form for simplicity.
By way of example, the radiation transorber may be 2-(p-(2-methyllactoyl)phenoxy)ethyl 1,3-dioxo-2-isoindoline-acetate s having the formula o ¢C~N--CH~ O(CH ) ~~3e~ ~CH3 phthaloylglycyl-cyclohexylphenyl ketone ester having the formula ~N--CH2--C--0~
~, 4-(4-oxyphenyl)-2-butanone- 1 -(4-(2-oxyethoxy)phenyl)-2-hydroxy-1S 2-methyl-propan- 1 -one (or 2-hydroxy-2-methyl-4'-(2-(p-(3-oxobutyl)phenoxy)ethoxy)-propiophenone) having the formula CH3--C--CH2CH2~O--CH2CH2--O~C--I OH
or CA 022194~0 1997-11-17 WO 96/39646 PCT/US96~ 7 4-(4-oxyphenyl)-2-butanonecyclohexyl-phenyl ketone (or 4-(p-((4-benzoylcyclohexyl)oxy)phenyl)-2-butanone) having the formula CH3~ ~H2CH2~30~
~0 Examples 6-8, and 13 describe methods of preparing the above radiation transorbers. It is to be understood that other sensitizers, photoreactors, and radiation transorbers than those specifically listed above may be used in the present invention.
Accordingly, the following formula represents a pre-dye wherein the dye molecule is a leuco form of crystal violet (N-(4-(Bis(4-(~limt-~hylamino)phenyl)methylen-2,5-cyclohexa-dien- l-ylidene)-N-methylmeth~n~minium chloride) covalently bonded to X, wherein X represents a radiation transorber, or wherein X represents a wavelength-specific sensitizer covalently bonded thereto, wherein the oxyethoxyphenyl group functions as a photoreactor.
,D~H3)2 N~--C~OCH2CH2O--X
N(CH3)2 A method of preparing the above pre-dye is described in Example 25.
_ WO 96/39646 PCI'/US96/08887 By way of example, the pre-dye may be, but is not limited to, the following formulas: =
IN(CH3)2 (CH3)2N ~ ~c O OCH2CH20CCH2--N~
N(CH3)2 N(CH3)2 C~¢l ~ ~N-cH2c 0 N(cH3)2 WO 96/39646 PCI'/US96/08887 ~H3)2 lC~3~(C"2)20C''2C(C"2)2 \=/ O(Cn2)20~3C--v~vn CH3 ¢~
N(CH3~2 N(CH3)2 1 ~3ll~o(cH2)2ocH2c(cH2)2~o~
CH3 ,J~, C=O
N(CH3)2 or ~H3)2 C~ 3 0~CHz)zO~ N--CH ~CO(CHz)zO~ lOc_c CHOJH
O
N(CH3)2 A method of preparing the following pre-dye is described in Example 26.
WO 96t39646 PCr/US96/08887 N(CH3)2 3o(cH2)2o~N--cH28o(cHz)2o~loc--c~cHH~H
N(CHs)z A desired pre-dye has the following formula:
N(CH3)2 (CH3)2N{~--?~ c OCH2CH20CCH2--N~X3 N(CH3)2 This particular structure shows the radiation transorber, 2-(p-(2-methyllactoyl)phenoxy)ethyl 1,3-dioxo-2-isoindolineacetate, attached to crystal violet (N-(4-(Bis(4-(dimethylamino)-phenyl)methylen-2,5-cyclohexedien- 1 -ylidene)-N-methyl-meth~n~minium chloride). Examples 1-3 describe how to prepare the above pre-dye molecule.
It is to be understood that the disclosed formulas are merely an example of the pre-dye concept that is considered part of the present invention and that other dyes can be substituted for the crystal violet and other radiation transorbers can be employed in substitution of the above radiation transorbers.
For example, the following are other pre-dyes of the present invention, wherein X represents a radiation transorber, and wherein R represents a hydrogen, methyl, or ethyl group.
WO 96t39646 PCT/US96~33 R2N~--C--X
~1 ~3~
F.x~mrle 27 describes a method for preparing the following lo pre-dye.
PCT/US96/Og'?fl7 R2N ~C--C--X
~C
Additional examples of other pre-dyes of the present invention include the following, wherein R represents an alkyl or aryl group.
Nl (CH3)2 (CH3)2N~ H CH3 N(cH3)2 CA 022l9450 l997-ll-l7 WO 96/39646 PCT/US9G/~.~3~ /
N(CH3)2 (CH3)2N ~--C--C=CI--R
N(cH3)2 N(cH3)2 (CH3)ZN~c~ 3CH2--~3 N(CH3)2 or CA 022194~0 1997-11-17 ~(CH3)2 ~ 1 11 (CE~3)~N--~ ~8~3 N(CH3)2 The present invention also relates to a method of forming a colored composition. The method comprises irradiating a composition containing a pre-dye. The pre-dye is a molecule comprising a dye molecule covalently attached to a radiation transorber. When the dye molecule is covalently ~tt~rh~-d to the radiation transorber, the composition is colorless. The method comprises exposing the pre-dye to ultraviolet radiation at a dosage lo level sufficient to mllt~te the dye. Example 4 further illustrates the method of forming a colored composition lltili7in~ the pre-dye of the present invention.
The pre-dye of the present invention can be irradiated with radiation having a wavelength of between about 4 to about 1,000 nanometers depen~lin~ upon the radiation transorber that is present in the composition. Thus, the radiation may be ultraviolet radiation, including near ultraviolet and far or vacuum ultraviolet radiation;
visible radiation; and near infrared radiation. Desirably, the pre-dye is irradiated with radiation having a wavelength of from about 4 to about 700 nanometers. More desirably, the pre-dye is irradiated with ultraviolet radiation having a wavelength of from about 4 to about 400 nanometers. It is more desirable that the radiation have a wavelength of between about 100 and 375 nanometers.
The present invention also relates to a substrate having an 2s image thereon that is formed by the pre-dye molecule of the present invention.
CA 022l94~0 l997-ll-l7 WO 96/39646 PCT/US~)6/0~7 Leuco Dye/~n~i~7tiQn Transorber Admucture In another embodiment of the present invention, the composition of the present invention includes an admixture of a conventional leuco dye and a radiation transorber. The leuco dye, in the presence of the radiation transorber, is adapted, upon exposure of the transorber to radiation, ~leferably ultraviolet radiation, to be mutable to a colored composition. The preferred radiation transorber is adapted to absorb ultraviolet radiation and interact with the leuco dye to effect the illevelsible mutation of the molecule to a colored composition.
The radiation transorbers that may be admixed with a leuco dye in the present invention are described above.
Leuco dyes that can be used in the present invention include, but are not limited to, aminotriarylmethanes, aminoxanthenes, aminothioxanthenes, amino-9, 1 0-dihydroacridines, ~minopheno~c~7.inl~s, aminophenothi~7inçs~ ~minodihydroph~n~7in~s, aminodiphenylmPth~nes, leuco in~l~mines, aminohydrocinn~mic acids (cyanoethanes, leucomethines), hydrazines, leuco indigoid dyes, amino-2,3-dihydroanthraquinones, phen~thyl~nilin~-s, 10-acyl-aminodihydrophen~7ines, 10-acyl-aminophenothi~7inPs, 10-acyl-aminophenoxazines and aminotriarylm~th~nes wherein the m~th~ne hydrogen has been replaced by an alkylthio, benzylthio, 2-phenylhydrazino, or alkoxycarbonyl group. The generally 2s preferred class of leuco dyes is the aminotriarylmethane class and derivatives thereof. The aminotriarylmethane dyes, as well as the other classes of dyes, are reviewed in Abrahart, E.N., Dyes and their Intermediates, Chemical Publishing Co., Inc., (1977) which is incorporated herein by lefelellce. The aminotriarylmethanes are reviewed at page 151 of the Abrahart reference. A desirable leuco dye is an aminotriarylmethane dye.
The present invention also includes forming a colored molecule from a leuco dye by admixing the leuco dye with a radiation transorber, and irr~ ting the adrnixture with certain wavelengths of electrom~gnçtic radiation.
CA 022194~0 1997-11-17 The leuco dye composition of the present invention can be irradiated with radiation having a wavelength of between about 4 to about 1,000 nanometers depending upon the radiation transorber that is present in the composition. Thus, the radiation may be ultraviolet s raA;ation, in~ iR~ near ultr~i~et a~d ~ cu~m ultraviolet radiation; visible radiation; and near infrared radiation. Desirably, the composition is irr~ ted with radiation having a wavelength of from about 4 to about 700 nanometers. More desirably, the composition of the present invention is irradiated with ultraviolet radiation having a wavelength of from about 4 to about 400 nanometers. It is more desirable that the radiation have a wavelength of between about 100 to 375 nanometers.
In another embodiment, the pre-dye composition is applied to a substrate before being irr~ ted with ultraviolet radiation. The present invention is also related to a substrate having an image thereon that is formed by the leuco dye composition of the present invention. It is desirable that the ....~ted dye is stable.
Although the leuco dye and the r~A~i~tion transorber have been described as separate compounds, they can be part of the same molecule, in which case the single molecule is desi~n~teA. a pre-dye.
For example, the dye and the radiation transorber can be covalently coupled to each other, either directly, or indirectly through a relatively small molecule or spacer. ~ltern~tively, the dye and radiation transorber can be covalently coupled to a large molecule, 2s such as an oligomer or a polymer. Further, the dye and radiation transorber may be associated with a large molecule by van der Waals forces, and hydrogen bonding, among other means. Other variations will be readily apparent to those having ordinary skill in the art.
The pre-dye and the leuco dye/radiation transorber admixtures of the present invention may optionally contain a molecular includant having a chemical structure which Aefin~s at least one cavity. Thus, the cavity in the molecular includant can be a tunnel through the molecular includant or a cave-like space or a dented-in space in the molecular includant. The cavity can be isolated or independent, or 3s connected to one or more other cavities.
CA 022194~0 1997-11-17 WO 96/39646 PCI'/US96/08887 The molecular includant can be inorganic or organic in nature.
In certain embo(lim~nts, the chemical structure of the molecular includant is adapted to form a molecular inclusion complex. The molecular includants include, but are not limited to, clathrates, zeolites, and cyclodç~trin~. Examples of cyclodextrins include, but are not limited to, a-cyclodextrin, ~-cyclofl~ctrin~ ~f-cyclodextrin, hydroxypropyl 13-cyclodextrin, hydroxyethyl ,~-cyclodextrin, sulfated ~-cyclodextrin, hydroxyethyl a cyclodextrin, carboxymethyle a cyclodextrin, carboxymethyl ~-cyclodextrin, carboxymethyl ~ cyclodextrin, octyl succinated a cyclodextrin, octyl succinated ~-cyclodextrin, octyl succinated ~ cyclodextrin and slllf~t~d ,13 and ~-cyclodextrin (American Maize-Products Company, ~mmond, Indiana).
The desired molecular includant is a cyclodextrin. More par~icularly, in some embo-limPnts, the desired molecular includant is an a-cyclodextrin. In other embo-lim~ntc, the desired molecular includant is a ~-cyclodextrin. In yet other embo~iim~nt~7 the desired molecular includant is ry-cyclodextrin.
In those embodiments where the leuco dye molecule and the radiation transorber are adrnixed, each of the leuco dye and radiation transorber is optionally associated with one or more molecular includants. In some emborlimPnt~, the leuco dye is at least partially included within a cavity of the molçc-ll~r inclu-l~nt and the radiation transorber is associated with the molecular includant outside of the cavity. In some embo~lim~nt~7 the radiation transorber is covalently coupled to the outside of the molecular includant.
For example, the leuco dye and/or the radiation transorber can be m~int~ined in close proximity to the molecular includant by hydrogen bonding, van der Waals forces, or the like. The term "associated", in its broadest sense, means that the leuco dye and the radiation transorber are at least in close proximity to the molecular includant. Alternatively, either or both of the leuco dye and the radiation transorber can be covalently bonded to the molecular includant. In certain embodiments, the leuco dye will be associated with the molecular includant by means of hydrogen bonding and/or CA 022194~0 1997-11-17 WO 96/39646 PCT/US!)6/08887 van der Waals forces or the like, while the radiation transorber is covalently bonded to the molec~ r incl~ nt In other embo-liment~, the leuco dye is at least partially included within the cavity of the molecular includant, and the radiation transorber is located outside of the cavity of the molecular includant. It is to be understood that one or more radiation transorbers may be associated with one molecular includant, one or more leuco dyes may be associated with one molecular includant, or one or more of both may be associated with one molecular includant. It is also to be understood that one or more pre-dyes may be associated with a molecular includant, or one pre-dye may be associated with more than one molecular includant.
In several embodiments, the radiation transorber molecule, the wavelength-selective sensitizer, or the photoreactor may be associated with a molecular includant. It is to be noted that the number of such molecules can be between approximately 1 and approY~tr.a~.ely 21 ~oleeul~ ~er ~l~ar in~ Of ~se, ifi certain situations, there can be more than 21 molecules per molecular includant molecule. Desirably, there are more than three of such molecules per molec~ r includant.
The degree of substitution of the functionalized molecular includant may be in a range of from 1 to approximately 21. As another example, the degree of substitution may be in a range of from 3 to about 10. As a further example, the degree of substitution may be in a range of from about 4 to about 9.
The leuco dye may be associated with the functionalized molecular includant. The term "associated" in its broadest sense means that the leuco dye is at least in close proximity to the function~li7e-1 molecular includant. For example, the leuco dye may be m~int~ined in close proximity to the functionalized molecular includant by hydrogen bonding, van der Waals forces, or the like.
Alternatively, the leuco dye may be covalently bonded to the ~ functionalized molecular includant, although this normally is neither desired nor necessary. As a further example, the leuco dye may be at least partially included within the cavity of the functionalized molecular includant.
CA 022194~0 1997-11-17 The ex~mples below disclose methods of ~repaLing and associ~ting colorants and ultraviolet radiation transorbers to ~-cyclo~e~trin~. For illustrative purposes only, F.~mples 6, 7, 11, and 12 disclose one or more methods of preparing and associating S colorants and ultraviolet radiation transorbers to cyclodextrins.
In those embodiments of the present invention in which the ultraviolet radiation transorber is covalently coupled to the molecular includant, the efficiency of energy transfer from the ultraviolet radiation transorber to the leuco dye is, at least in part, a function of the number of ultraviolet radiation transorber molecules which are ~tt~f hPd to the molecular includant.
Accordingly, the present invention also relates to a composition which includes a leuco dye and a functionalized molecular incl~ nt For illustrative purposes only, Examples 14 1S through 21, and 23 through 24 disclose other methods of preparing and associating colorants and ultraviolet radiation transorbers to cyclodextrins, wherein more than two molecules of the ultraviolet radiation transorber are covalently coupled to each molecule of the molecular includant.
The present invention also provides a method of making a functionalized molecular includant. The method of m~king a functionalized molecular includant involves the steps of providing a derivatized ultraviolet radiation transorber having a nucleophilic group, providing a derivatized molecular includant having more than 2s two leaving groups per molecule, and reacting the derivatized ultraviolet radiation transorber with the derivatized molecular includant under conditions sufficient to result in the covalent coupling of an average of more than two ultraviolet radiation transorber molecules to each molecular includant molecule. By way of example, the derivatized ultraviolet radiation transorber may be 2-[p-(2-methyl-2-mercaptomethylpropionyl)phenoxy~ethyl 1,3-dioxo-2-isoindoline-acetate. As another example, the derivatized ultraviolet radiation transorber may be 2-mercaptomethyl-2-methyl-4'-[2-[p-(3-oxobutyl)phenoxy]ethoxy]propiophenone.
CA 022l94~0 l997-ll-l7 In general, the derivatized ultraviolet radiation transorber and the derivatized molecular includant are selected to cause the covalent coupling of the ultraviolet radiation transorber to the molecular includant by me7lns of a bimolecular nucleophilic substitution reaction. Consequently, the choice of the nucleophilic group and the leaving groups and the preparation of the derivatized ultraviolet radiation transorber and derivatized molecular includant, respectively, may be readily accomplished by those having ordinary skill in the art without the need for undue experimentation.
The nucleophilic group of the derivatized ultraviolet radiation transorber may be any nucleophilic group capable of participating in a bimolec~ r nucleophilic substitution reaction, provided, of course, that the reaction results in the covalent coupling of more than two molecules of the ultraviolet radiation transorber to the molecular incl~ nt The nucleophilic group generally will be a Lewis base, i.e., any group having an unshared pair of electrons. The group may be neutral or negatively charged. Examples of nucleophilic groups include, by way of illustration only, aliphatic hydroxy, aromatic hydroxy, alkoxides, carboxy, carboxylate, amino, and mercapto.
Similarly, the leaving group of the derivatized molecular includant may be any leaving group capable of participating in a bimolecular nucleophilic substitution reaction, again provided that the reaction results in the covalent coupling of more than two molecules of the ultraviolet radiation transorber to the molecular includant. Fx~mples of leaving groups include, also by way of illustration only, p-toluenesulfonates (tosylates), p-bromobenzenesulfonates (brosylates), p-nitrobenzenesulfonates (nosylates), methanesulfonates (mesylates), oxonium ions, alkyl perchlorates, ammonioalkane sulfonate esters (betylates), alkyl fluorosulfonates, trifluoromethanesulfonates (triflates), nonafluorobutanesulfonates (nonaflates), and 2,2,2-trifluoroethanesulfonates (tresylates).
The reaction of the derivatized ultraviolet radiation transorber with the derivatized molecular includant is carried out in solution.
The choice of solvent depends upon the solubilities of the two CA 022194~0 1997~ 17 SUBSTrruTE SHEET
.... ..... .. . - . .. .
derivatized species. As a practical matter, a particularly useful solvent is N,N-dimethylforrnamide (DMF).
The reaction conditions, such as temperature, reaction time, and the like generally are matters of choice based upon the natures of the nucleophilic and leaving groups. Elevated temperatures usually are not required. For example, the reaction temperature may be in a range of from about 0~C to around ambient temperature, i.e., to 20~-25~C.
The preparation of the functionalized molecular includant as described above generally is carried out in the absence of the colorant or leuco dye. However, the leuco dye may be associated with the derivatized molecular includant before reacting the derivatized ultraviolet radiation transorber with the derivatized moiecular includant, particularly if a degree of substitution greater than about three is desired. When the degree of substitution is about three, it is believed that the association of the leuco dye with the functionalized molecular includant still may permit the leuco dye to be at least partially included in a cavity of the functionalized molecular includant. At higher degrees of substitution, such as about six, steric hindrance may partially or completely prevent the leuco dye from being at least partially included in a cavity of the functionalized molecular includant. Consequently, the leuco dye may be associated with the derivatized molecular includant which 2s normally will exhibit little, if any, steric hindrance. In this instance, the leuco dye will be at least partially included in a cavity of the derivatized molecular includant. The above-described bimolecular nucleophilic substitution reaction then may be carried out to give a composition of the present invention in which a leuco dye is at least partially included in a cavity of the functionalized mol~ular ir~cllx~rlt.
Example 5 describes a method of producing color by irr~ ing a leuco dye admixed with a radiation transorber attached to a ~-cyclodextrin.
The present invention is further described by the examples which follow.
..
~, SUBSTITUTE ~HEET . . ~ , ,"., In the examples, all parts are parts by weight unless stated otherwise.
~mrle I
Preparation of a pinacol type starting material.
The starting material for the pre-dye molecule which will have a blue color when irradiated is prepared according to the following reaction:
(cH3)2N O--CH2CH2,0H
C=O + O=C ~ Mg (C 13)2N 1 HgC12N(CH3)2 (CH3)~N N(CH3)2 OH OH '~ OCH2CH2OH
In a S00 ml round bottom 3-necked flask fitted with a magnetic stir bar, condensor, addition funnel was placed 10 g (0.037 mole) bis dimethylaminobenzophenone (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin), 1 g hydroxy ethoxy-dimethyl amino benzophenone (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin) and 0.75 g magnesium shavings (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin). 200 ml of anhydrous benzene was poured into the reaction mixture and was heated to 50~C and 0.84 g of mercury chloride in 20 ml benzene was slowly added ~~)~o S~
WO 96/39646 PCT/US9G,'1~9 9 ~7 over 20 minutes. The reaction was initi~te~l by ~ ling a small crystal of iodine to the flask. The reaction mixture was heated for 30 minutes. The organic layer was separated, dried and the solvent removed under reduced pressure to yield a yellow solid. The product s was run on a short silica column with 50% ethyl ~cet~t~ in hexane as solvent.
Mass Spec: 538 (m+-OH), 521, 480, 252 ~mple 2 The product from Fx~mple 1 was treated according to the following reaction:
(cH3)2N N(CH3)2 (CH3)2N-- --C_C~ }OCH2CH20H
N(CH3)2 ~0 (CH3)2N CbC O OCH2CH20H
N(CH3)2 1S To a 250 ml round bottomed flask was added 5.0 g (9 mmole) of the diol from Example 1, and a magnetic stir bar. 50 ml of 50%
concentrated sulfuric acid in water was added and the reaction mixtl-re stirred in an ice bath for 1 hour. The pH of the reaction WO96/39646 PCr/US96 mixture was then brought up to approximately 7.0 by addition of sodium hydroxide. The precipitate was filtered and dried under v~c~ m for 2 hours. The yield was 4.2 g (88%).
Mass Spec: 537 (m+), 520, 448, 433 F,x~mple 3 The product from Example 2 was subjected to the following reaction:
N(CH3)2 (CH3)2N~C~-C~30CH ~CH20H + HOzCClI2--N~
N(CH3)2 Rçn7Pn~-Tosyl Acid ~(CH3)2 (cH3)2N~co{~ocHzcH2occH2-N~3 N(cH3)2 In a 250 ml round bottom flask fitted with a m~gnetic stir bar, Dean & Stark adaptor and condensor was added 4.0 g (7.6 mmole) ketone from Example 2, 1.5 g phthaloylglycine (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin), O.lgp-toluenesulphuric acid (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin) and 100 ml of anhydrous benzene (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin). The reaction mixture was heated at reflux for 8 hours after which time 0.3 ml of water had been collected in the adaptor. Removal of the solvent under reduced pressure gave 5.0 g of product.
t CA 022194~0 1997-11-17 SUBSTlTUTE SHEl~T
28 ~ ~ ..................... ..
Example 4 0.2 g of the product from Example 3 compound was dissolved in 5 ml of acetonitrile (Fisher Scientific, Pittsburgh, Pennsylvania). 3 drops of the mixture was placed on a metal plate (Q-panel) and spread out with the aid of a spatula. The plate was then exposed to 222 nm excimer radiation at 12.19 m/minute (40 ft/minute) on the conveyer. A deep blue color developed on radiation.
Four drops were placed on a sheet of white paper (Neenah bond) and allowed to spread out. The moist sheet was then exposed to 222 nm excimer radiation. The moist area turned a deep blue in color.
Example 5 A leuco dye (leuco crystal violet) (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin) was mixed with a composition comprising a radiation transorber attached to a ,13-cyclodextrin represented by the following formula:
~-cyclodextrin ~(~2CH2 ~ C~2~N--CH,C--o(C~2).o~3~ C~ ]
The synthesis of the radiation transorber attached to a ,13-cyclodextrin is described in Examples 8-11, and in copending U.S. Patent Application Serial No. 08/461,372 filed on June 5, 1995 and incorporated herein by reference. O.lg leuco crystal violet dye and 0.2 g a radiation transorber attached to a ,(3-cyclodextrin was mixed in 5 ml acetonitrile (Fisher Scientific, Pittsburgh, Pennsylvania). The colorless solution was placed on a metal plate (Q-panel) and spread out with a spatula (approximately 5 drops of solution). The plate was passed under the 222 nm excimer lamp. (10.67 m/minute (35 ft/minute) on the conveyer) after which the solution had turned a deep blue in color. This was repeated by putting 3 drops onto paper (Neenah Bond) and oSt~E
CA 022194~0 1997-11-17 29.
spreading it with a spatula. Passing the moist paper under a 222 nm dielectric barrier discharge excimer lamp (Haraus Noblelight AG, Hanau, Gerrnany) developed a blue color. Leuco dye by itself did not develop any color on irradiation with 222 nm.
s ~mrle 6 This example describes the preparation of a b-cyclodextrin molecular includant having (1) an ultraviolet radiation transorber covalently bonded to the cyclodextrin outside of the cavity of the cyclodextrin, and (2) a colorant associated with the cyclodextrin by means of hydrogen bonds and/or van der Waals forces.
A. Friedel-Crafts Acylation of Transorber A 250-ml, three-necked, round-bottomed reaction flask was fitted with a contlçn~er and a pressure-eqll~li7ing addition funnel equipped with a nitrogen inlet tube. A magnetic stirring bar was placed in the flask. While being flushed with nitrogen, the flask was charged with 10 g (0.05 mole) of l-hydroxycyclohexyl phenyl ketone (IRGACURE 184, Ciba-Geigy Corporation, Hawthorne, New York), 100 ml of anhydrous tetrahydofuran (Aldrich Chemical Company, Inc., Milw~lk~e, Wisconsin), and 5 g (0.05 mole) of succinic anhydride (Aldrich Chemical Co., Milwaukee, WI). To the continuously stirred contents of the flask then was added 6.7 g of anhydrous aluminum chloride (Aldrich Chemical Co., Milw~llkt-e, Wisconsin). The resulting reaction llli~l~e was m~int~ined at about 0~C in an ice bath for about one hour, after which the ll.~Lule was allowed to warm to ambient temperature for two hours. The reaction mixture then was poured into a mixture of 500 ml of ice water and 100 ml of diethyl ether. The ether layer was removed after the addition of a small amount of sodium chloride to the aqueous phase to aid phase separation. The ether layer was dried over anhydrous m~gn~sium sulfate. The ether was removed under reduced pressure, leaving 12.7 g (87 percent) of a white crystalline powder. The m~teri~l was shown to be l-hydroxycyclohexyl 4-(2-CA 022194~0 1997-11-17 carboxyethyl)carbonylphenyl ketone by nuclear m~gnetic resonance analysis.
B. Preparation of Acylated Transorber Acid Chloride A 250-ml round-bottomed flask fitted with a condenser was charged with 12.0 g of l-hydroxycyclohexyl 4-(2-carboxyethyl)carbonylphenyl ketone (0.04 mole), 5.95 g (0.05 mole) of thionyl chloride (Aldrich Chemical Co., Milwaukee, Wisconsin), and 50 ml of diethyl ether. The resulting reaction mixture was stirred at 30~C for 30 minutes, after which time the solvent was removed under reduced pressure. The residue, a white solid, was maintained at 0.01 Torr for 30 minlltes to remove residual solvent and excess thionyl chloride, leaving 12.1 g (94 percent) of 1-hydroxycyclohexyl 4-(2-chloroformylethyl)carbonylphenyl ketone.
C. Covalent Bonding of Acylated Transorber to Cyclodextrin A 250-ml, three-necked, round-bottomed reaction flask containing a m~gnetic stirring bar and fitted with a thermometer, condenser, and pressure-eq~l~li7ing addition funnel equipped with a nitrogen inlet tube was charged with 10 g (9.8 mmole) of ~-cyclodextrin (American Maize-Products Company, Hammond, Indiana), 31.6 g (98 mmoles) of l-hydroxycyclohexyl 4-(2-chloroformylethyl)carbonylphenyl ketone, and 100 ml of N,N-~lim~thylforrn~mide while being continuously flushed with nitrogen.
The reaction mixture was he~tP~ to 50~C and 0.5 rnl of triethyl~min~
added. The reaction ~ u~e was m~int~in~rl at 50~C for an hour and allowed to cool to ambient temperature. In this preparation, no ~ttempt was made to isolate the product, a ~-cyclodextrin to which an ultraviolet radiation transorber had been covalently coupled (referred to hereinafter for convenience as ~-cyclodextrin-transorber).
The foregoing procedure was repeated to isolate the product of the reaction. At the conclusion of the procedure as described, the reaction mixture was concentrated in a rotary evaporator to roughly 10 percent of the original volume. The residue was poured into ice CA 022194~0 1997-11-17 water to which sodium chloride then was added to force the product out of solution. The resulting precipitate was isolated by filtration and washed with diethyl ether. The solid was dried under reduced pressure to give 24.8 g of a white powder. In a third ~e~a~dtion, the residue rem~ining in the rotary evaporator was placed on top of an approximately 7.5-cm column cont~ining about 15 g of silica gel.
The residue was eluted with N,N-~lim~thylform~mide, with the eluant being monitored by me~n.s of Wh~tm~n(~) Flexible-Backed TLC
Plates (Catalog No. 05-713-161, Fisher Scientific, Pittsburgh, Pennsylvania). The eluted product was isolated by evaporating the solvent. The structure of the product was verified by nuclear m~gnetic resonance analysis.
D. Association of Colorant with Cyclodextrin-Transorber-Preparation of Colored Composition To a solution of 10 g (estim~tt~l to be about 3.6 mmole) of ~-cyclodextrin-transorber in 150 ml of N,N-dimethylform~mide in a 250-ml round-bottomed flask was added at ambient temperature 1.2 g (3.6 mmole) of Malachite Green oxalate (Aldrich Chemical Company, Inc., Milw~llk~e7 Wisconsin), lefelled to hereinafter as Colorant A for convenience. The reaction mixture was stirred with a m~gnetic stirring bar for one hour at ambient temperature. Most of the solvent then was removed in a rotary evaporator and the residue was eluted from a silica gel column as already described.
The ~-cyclodextrin-transorber Colorant A inclusion complex moved down the column first, cleanly separating from both free Colorant A
and ~-cyclodextrin-transorber. The eluant cont~ining the complex was collected and the solvent removed in a rotary evaporator. The residue was subjected to a reduced pressure of 0.01 Torr to remove ~ 30 residual solvent to yield a blue-green powder.
- E. Mutation of Colored Composition The ~-cyclodextrin-transorber Colorant A inclusion complex was exposed to ultraviolet radiation from two different lamps, Lamps A and B. Lamp A was a 222-nanometer excimer lamp assembly organized in banks of four cylindrical lamps having a CA 022194~0 1997-11-17 WO 96/39646 PCI'/US96/08887 length of about 30 cm. The lamps were cooled by circ~ ting water through a centrally located or inner tube of the lamp and, as a consequence, they operated at a relatively low temperature, i.e., about 50~C. The power density at the lamp's outer surface typically is in 2he range of from about 4 to about 20 joules per square meter (J/m ). However, such range in reality merely reflects the capabilities of current excimer lamp power supplies; in the future, higher power ~len~itie~ may be practical. The distance from the lamp to the sample being irr~ ted was 4.5 cm. Lamp B was a 500-watt Hanovia medium pressure mercury lamp (Hanovia Lamp Co., Newark, New Jersey). The distance from Lalnp B to the sample being irradiated was about 15 cm.
A few drops of an N,N--limP*hylformamide solution of the ~-cyclodextrin-transorber Colorant A inclusion complex were placed on a TLC plate and in a small polyethylene weighing pan. Both s~mples were exposed to Lamp A and were decolorized (mllt~te~ to a colorless state) in 15-20 seconds. Similar results were obtained with Lamp B in 30 seconds.
A first control sample consisting of a solution of Colorant A
and ~-cyclo-ipxtrin in N,N--limPthylform~mide was not decolorized by Lamp A. A second control sample consisting of Colorant A and l-hydroxycyclohexyl phenyl ketone in N,N-dimethylformamide was decolorized by Lamp A within 60 seconds. On standing, however, the color began to re~ear within an hour.
2s To evaluate the effect of solvent on decolorization, 50 mg of the ~-cyclodextrin-transorber Colorant A inclusion complex was dissolved in 1 ml of solvent. The resulting solution or ~ ~e was placed on a glass microscope slide and exposed to Lamp A for 1 minute. The rate of decolorization, i.e., the time to render the sample colorless, was directly proportional to the solubility of the complex in the solvent, as sllmm~ri7ed below.
CA 022194~0 1997-11-17 Table 1 Solvent Solubility Decolorization Time N,N-Dimethylform~mide Poor 1 ~ e Dimethylsulfoxide Soluble <10 seconds Acetone Soluble <10 seconds Hexane Insoluble --Ethyl Acetate Poor 1 ~ llule Finally, 10 mg of the ~-cyclodextrin-transorber Colorant A
inclusion complex were placed on a glass microscope slide and crushed with a pestle. The resulting powder was exposed to Lamp A
for 10 seconds. The powder turned colorless. Similar results were obtained with Lamp B, but at a slower rate.
Example 7 Because of the possibility in the preparation of the colored composition described in the following examples for the acylated transorber acid chloride to at least partially occupy the cavity of the cyclodextrin, to the partial or complete exclusion of colorant, a modified preparative procedure was carried out. Thus, this example describes the preparation of a ~-cyclodextrin molecular includant having (1) a colorant at least partially included within the cavity of the cyclodextrin and associated therewith by means of hydrogen bonds and/or van der Waals forces, and (2) an ultraviolet radiation transorber covalently bonded to the cyclodextrin subst~nti~lly outside of the cavity of the cyclodextrin.
A . Association of Colorant with a Cyclodextrin To a solution of 10.0 g (9.8 mmole) of ~-cyclodextrin in 150 ml of N,N--lim~thylformamide was added 3.24 g (9.6 mmoles) of Colorant A. The resulting solution was stirred at ambient temperature for one hour. The reaction solution was concentrated under reduced pressure in a rotary evaporator to a volume about one-tenth of the original volume. The residue was passed over a CA 022194~0 1997-11-17 WO 96/39646 PCT/US~6/08887 silica gel column as described in Part C of Fx~mple 6. The solvent in the eluant was removed under reduced pressure in a rotary evaporator to give 12.4 g of a blue-green powder, ~-cyclodextrin Colorant A inclusion complex.
B. Covalent Bonding of Acylated Transorber to Cyclodextrin Colorant Inclusion Complex - Preparation of Colored Composition A 250-ml, three-necked, round-bottomed reaction flask containing a m~netic stirring bar and fitted with a thermometer, condenser, and pressure-eqll~li7in~ addition funnel equipped with a nitrogen inlet tube was charged with 10 g (9.6 mmole) of ~-cyclodextrin Colorant A inclusion complex, 31.6 g (98 mmoles) of l-hydroxycyclohexyl 4-(2-chloroformylethyl)carbonylphenyl ketone prepared as described in Part B of F.x~mple 6, and 150 ml of N,N-dimethylform~mide while being continuously flushed with nitrogen. The reaction mixture was he~tefl to 50~C and 0.5 ml of triethyl~mine added. The reaction mixtllre was m~int~in~-l at 50~C
for an hour and allowed to cool to ambient temperature. The reaction mixture then was worked up as described in Part A, above, to give 14.2 g of 13-cyclodextrin-transorber Colorant A inclusion complex, a blue-green powder.
C. Mutation of Colored Composition The procedures described in Part E of Example 6 were repeated with the ~-cyclo-lextrin-transorber Colorant A inclusion complex prepared in Part B, above, with essçnti~lly the same results.
li x~mple 8 This example describes a method of preparing an ultraviolet radiation transorber, 2-[p-(2-methyllactoyl)phenoxy]ethyl 1,3-dioxo-2-isoindolin~f etate, design~t~l phthaloylglycine-2959.
The following was admixed in a 250 ml, three-necked, round bottomed flask fitted with a Dean & Stark adapter with condenser and two glass stoppers: 20.5g (0.1 mole) of the wavelength selective sensitizer, phthaloylglycine (Aldrich Chemical Co., Milwaukee, WO 96~9646 PCT~US96/08887 Wisconsin); 24.6 g (0.lmole) of the photoreactor, DARCUR 2959 (Ciba-Geigy, Hawthorne, New York); 100 ml of ben~ene (Aldrich Chemical Co., Milw~llk~e7 Wisconsin); and 0.4 g p-toluenesulfonic acid (Aldrich Chemical Co., Milw~llk~e, Wisconsin). The rnixture S was heated at reflux for 3 hours after which time 1.8 ml of water was collected. The solvent was removed under reduced pressure to give 43.1 g of white powder. The powder was recryst~lli7e~1 from 30% ethyl ~cet~te in hexane (Fisher) to yield 40.2 g (93%) of a white crystalline powder having a mP.l~ing point of 153-4~C. The reaction is sllmm~ri7çd as follows:
~N{~H2co2H ~ HO--(CH2)2--~~ /CH3 p-toluene CH3 O sulfonic acid Benzene ~N--CH2C--O(cHJ2o~c\cc~H3H
The resulting product, designated phthaloylglycine-2959, had the following physical parameters:
IR [NUJOL MULL] vm~ 3440, 1760, 1740, 1680, 1600 cm-l lH NMR [CDC13] appm 1.64[s], 4.25[m], 4.49[m], 6.92[m3, 7.25[m], 7.86[m], 7.98[m], 8.06[m] ppm ~ 20 Example 9 ~ This example describes a method of dehydrating the phthaloylglycine-2959 produced in Example 8.
The following was admixed in a 250 ml round bottomed flask 2s fitted with a Dean & Stark adapter with condenser: 21.6 g (0.05 mole) phthaloylglycine-2959; 100 ml of ~nhydrous ben7P-ne (Aldrich Chemical Co., Milwaukee, Wisconsin); and 0.1 g p-toluenesulfonic acid (Aldrich Chemical Co., Milwaukee, Wisconsin). The mi~
was refluxed for 3 hours. After 0.7 ml of water had been collected in the trap, the solution was then removed under v~c~mm to yield 20.1 g (97%) of a white solid. However, analysis of the white solid showed that this reaction yielded only 15 to 20% of the desired dehydration product. The reaction is sl-mm~ri7e-1 as follows:
o XN ~H2C ~(CH2)20 ~e ~ C OH
p- toluerle sulfonic acid Benzene o G~N~H2C ~(CH2)2O~O CH;
The resulting reaction product had the following physical parameters:
IR (NUJOL) vma" 1617cm-1 (C=C-C=O) 1~
Example 10 This example describes the Nohr-MacDonald elimin~tion reaction used to dehydrate the phthaloylglycine-2959 produced in Example 8.
Into a 500 ml round bottomed flask were placed a stirring m~gnet, 20.0g (0.048 mole) of the phthaloylglycine-2959, and 6.6 g (0.048 mole) of anhydrous zinc chloride (Aldrich Chemical Co., Milwaukee, Wisconsin). 250 ml of anhydrous p-xylene (Aldrich Chemical Co., Milwaukee, Wisconsin) was added and the mixture refluxed under argon atmosphere for two hours. The reaction mixture was then cooled, resulting in a white precipitate which was collected. The white powder was then recryst~lli7e~1 from 20~o ethyl acetate in hexane to yield 18.1 g (95%) of a white powder. The reaction is ~ l ;7e-l as follows:
¢~N--CH2C--O(CH2)2~~ /CH3 H20 ZnCI2 ~
~,, p-Xylene ¢~N~H2C--O(CH2)2~~ ,~CH2 The resulting reaction product had the following physical lo parameters:
Melting Point: 138~C to 140~C.
Mass spectrum: m/e: 393 M +, 352, 326, 232, 160.
IR (KB) vm"" 1758, 1708, 1677, 1600 cm-l lH NMR [DMSO] ~ppm 1.8(s), 2.6(s), 2.8 (d), 3.8 (d), 4.6 (m), 4.8 (m), 7.3(m), 7.4 (m), 8.3 (m), and 8.6 (d) 13C NMR [DMSO] appm 65.9 (CH2=) Example 11 This example describes a method of producing a 13--cyclodextrin having dehydrated phthaloylglycine-2959 groups from Example 9 or 10 covalently bonded thereto.
The following was admixed in a 100 ml round-bottomed flask:
5.0 g (4 mmole) ,3--cyclodextrin (American Maize Product Company, Hammond, Indiana) (designated 13--CD in the following reaction); 8.3 g (20 mmole) dehydrated phthaloylglycine-2959; 50 ml of anhydrous DMF; 20 ml of benzene; and 0.01 g p--tolulenesulfonyl chloride (Aldrich Chemical Co., Milwaukee, Wisconsin). The mixture was chillP~l in a salt/ice bath and stirred for 24 hours. The reaction mixture was poured into 150 ml of weak sodium bicarbonate solution and extracted three times with 50 ml S ethyl ether. The aqueous layer was then filtered to yield a white solid comprising the ,3--cyclodextrin with phthaloylglycine-2959 group ~tt~he~l A yield of 9.4 g was obt~inlo~ Reverse phase TLC
plate using a 50:50 DMF:acetonitrile mixture showed a new product peak compared to the starting m~teri~
cyclodextrin H2C ~xCH2)20~ ~ <!H + _,~
HO--CH2'CH2/
.. ,i3 cyclodextrin ~c ~J
fl R ~H2 o--CH2~H2~
b~,~ ffH2C~)(CH2)20 ~ -~H~3H3 The ~-cyclodextrin molecule has several primary alcohols and secondary alcohols with which the phthaloylglycine-2959 can react.
1~ The above representative reaction only shows a single phthaloylglycine-2959 molecule for illustrative purposes.
Example 12 This example describes a method of assoc i~ting a colorant and an ultraviolet radiation transorber with a molecular includant. More particularly, this example describes a method of associating the colorant crystal violet with the molecular includant ,B--cyclodextrin covalently bonded to the ultraviolet radiation transorber dehydrated phthaloylglycine-2959 of Example 11.
CA 022194~0 1997-11-17 WO 96/39646 PCT/US96~1~5~g37 The following was placed in a 100 ml beaker: 4.0 g ,13--cyclodextrin having a dehydrated phthaloylglycine-2959 group; and 50 ml of water. The water was heated to 70~C at which point the solution becam~ clear. Next, 0.9 g (2.4 rnmole) crystal violet (Aldrich C'hPmical Company, Milwaukee, Wisconsin) was added to the solution, and the solution was stirred for 20 minntes. Next, the solution was then filtered. The filtrand was washed with the filtrate and then dried in a vacuum oven at 84~C. A violet-blue powder was obtained having 4.1 g (92%) yield. The resulting reaction product had the following physical parameters:
U.V. Spectrum DMF vm~ 610 nm (cf cv vm,~" 604 nm) ~y~mple 13 This example describes a method of producing the ultraviolet radiation transorber 4(4-hydroxyphenyl) butan-2-one-2959 (chloro substituted).
The following was admixed in a 250 ml round-bottomed flask fitted with a condenser and m~netic stir bar: 17.6 g (O.lmole) of the wavelength selective sen~iti7er~ 4(4-hydroxyphenyl) butan-2-one (Aldrich Chemical Company, Milwaukee, Wisconsin); 26.4 g (0.1 mole) of the photoreactor, chloro substituted DARCUR 2959 (Ciba-Geigy Corporation, Hawthorne, New York); 1.0 ml of pyridine (Aldrich Chemical Company, Milwaukee, Wisconsin); and 100 ml of anhydrous tetrahyd~orul~n (Aldrich Chemical Company, Milwaukee, Wisconsin). The mixture was refluxed for 3 hours and the solvent partially removed under reduced pressure (60% taken off). The reaction mixture was then poured into ice water and extracted with two 50 ml aliquots of diethyl ether. After drying over anhydrous magnesium sulfate and removal of solvent, 39.1 g of white solvent ~ 30 remained. Recryst~11i7~tion of the powder from 30% ethyl acetate in hexane gave 36.7 g (91%) of a white crystalline powder, having a melting point of 142-3~C. The reaction is sllmm~rized in the following reaction:
, WO 96/39646 PCI~/US96/~3~3~37 1~l ~OH + Cl(CH )~--~~cR ,CH3 CH3 ~--CH2CH2 ~~--(CH2)2_o~! CH3 The resulting reaction product had the following physical parameters:
IR [NUJOL MULL ] vm"c 3460, 1760, 1700, 1620, 1600 cm-l lH [CDCl3] appm 1.62[s],4.2[m], 4.5[m], 6.9tm] ppm The ultraviolet radiation transorber produced in this example, 4(~hydroxyphenyl) butan-2-one-2959 (chloro substituted), may be associated with ,B--cyclodextrin and a leuco dye such as the leuco form of crystal violet, using the methods described above wherein 4(4-hydroxyphenyl) butan-2-one-2959 (chloro substituted) would be substituted for the dehydrated phthaloylglycine-2959.
Example 14 Preparation of epoxide intermediate of dehydrated phthaloylglycine-The epoxide interm~ tP of dehydrated phthaloylglycine 2959 was ~ ared according to the following reaction:
CA 022l9450 l997-ll-l7 ~N--CH2C--o(cH2)2o~3lo--c,'cH;
H202/NaOH
~N--CH2 11--o(CH2)20 ~3C~o, ,CH;
In a 250 ml, three-necked, round bottomed flask fitted with an addition funnel, thermometer and magnetic stirrer was placed 30.0g (0.076 mol) of the dehydrated phthaloylglycine-2959, 70 ml methanol and 20.1 ml hydrogen peroxide (30% solution). The reac~ion rnixture was stirred and cooled in a water/ice bath to maintain a temperature in the range 15~-20~ C. 5.8 ml of a 6 N
NaOH solution was placed in the addition funnel and the solution was slowly added to m~int~in the reaction mixture tempei~LL~Ile of 15~-20~ C. This step took about 4 minlltes. The mixture was then stirred for 3 hours at about 20~-25~ C. The reaction mixtllre was then poured into 90 ml of water and extracted with two 70 ml portions of ethyl ether. The organic layers were combined and washed with 100 1~ ml of water, dried with anhydrous MgSO4 filtered, and the ether removed on a rotary evaporator to yield a white solid (yield 20.3g, 65%). The IR showed the stretching of the C-O-C group and the m~te.ri~l was used without further purification.
WO 96/:S9646 PCT/US96/08887 Example 15 Attachment of epoxide intermeL~ te to thiol cyclodextrin The ~tt~chm~nt of the epoxide intermP~ te of dehydrated phthaloylglycine 2959 was done according to the following reaction:
~N - cH2~--O(CH2)2~~H2 ~ - ,~
~ (HS--CH2CH
DMF
r 0~C Beta-CD
O o ocH3 [~N- CH2C--O(CH2)20~-CI H--CH2--(S--CH2CH2~
In a 250 ml 3-necked round bottomed flask fitted with a stopper and two glass stoppers, all being wired with copper wire and attached to the flask with rubber bands, was placed 30.0 g (0.016 mol) thiol cyclodextrin and 100 ml of ~nhydrous ~1imPIl-ylro~ mide (DMF) (Aldrich Chemical Co., Milwaukee, Wisconsin). The reaction mixture was cooled in a ice bath and 0.5 ml diisopropyl ethyl amine was added. Hydrogen sulfide was bubbled into the flask and a positive pressure m~int~in~.d for 3 hours. During the last hour, the reaction mixture was allowed to wa~n to room temperature.
The reaction mixture was flushed with argon for 15 minutes and then poured into 70 ml of water to which was then added 100 ml acetone. A white precipitate occurred and was filtered to yield 20.2 g (84.1%) of a white powder which was used without further purification.
In a 250 ml round bottomed flask fitted with a m~nP~ic stirrer and placed in an ice bath was placed 12.7 (0.031 mol), 80 ml of anhydrous DMF (Aldrich Chemical Co., Milwaukee, Wisconsin) and 15.0 g (0.010 mol) thiol CD. After the reaction l~ Lure was cooled, CA 022194~0 1997-11-17 0.5 ml of diisopropyl ethyl amine was added and the reaction mixtllre stirred for 1 hour at 0~C to 5~C followed by 2 hours at room temperature. The reaction mixture was then poured into 200 ml of ice water and a white precipitate formed immediately. This was filtered and washed with acetone. The damp white powder was dried in a convection oven at 80~C for 3 hours to yield a white powder. The yield was 24.5 g (88%).
Example 16 Insertion of Victoria Pure Blue in the cyclodextrin cavity In a 250 ml Erlenmeyer flask was placed a m~gn~tic stirrer, 40.0 g (0.014 mol) of the compound produced in Example 15 and 100 ml water. The flask was heated on a hot plate to 80~C. When the white cloudy mixture became clear, 7.43 g (0.016 mol) of lS Victoria Pure Blue BO powder was then added to the hot solution and stirred for 10 minutes then allowed to cool to 50~~. The contents were then filtered and washed with 20 ml of cold water.
The precipitate was then dried in a convention oven at 80~C
for 2 hours to yield a blue powder 27.9 g (58.1%).
Example 17 The preparation of a tosylated cyclodextrin with the dehydroxy phthaloylglycine 2959 attached thereto is performed by the following reactions:
2~
CA 022194~0 1997-11-17 WO 96/39646 PCI~/US96/08887 44 ' ~N--CH2C--O(CH2)2~~ ~CH2 ~,, DMF
¢~N--CH2C--O(CH2)2~~ ~CH2--S H
To a 500 ml 3-necked round bottomed flask fitted with a bubble tube, condenser and addition funnel, was placed 10 g (0.025 mole) of the dehydrated phthaloylglycine 2959 in 150 ml of anhydrous N,N-diethylformamide (Aldrich Chemical Co., Milwaukee, Wisconsin) cooled to 0~C in an ice bath and stirred with a m~gnetic stirrer. The synthesi~ was repeated except that the flask was allowed to warm up to 60~C using a warm water bath and the lo H2S pumped into the reaction flask till the stoppers started to move (trying to release the pressure). The flask was then stirred under these conditions for 4 hours. The saturated solution was kept at a positive pressure of H2S. The stoppers were held down by wiring and rubber bands. The reaction mixture was then allowed to warm-up overnight. The solution was then flushed with argon for 30 minutes and the reaction mixture poured onto 50 g of crushed ice and extracted three times (3 x 80 ml) with diethyl ether (Aldrich Chemical Co., Milwaukee, Wisconsin).
The organic layers were condensed and washed with water and dried with MgSO4. Removal of the solvent on a rotary evaporator gave 5.2 g of a crude product. The product was purified on a silica column using 20% ethyl acetate in hexane as eluant. 4.5 g of a white solid was obt~inP~1 A tosylated cyclodextrin was prepared according to the following reaction:
~c 7 CH3~CI
Pyridine ~, ,,~ CH2 [OTs~c To a 100 ml round bottomed flask was placed 6.0 g S ~-cyclodextrin (American Maize Product Company), lO.Og (0.05 mole) p-toluenesulfonyl chloride (Aldrich Chernical Co., Milwaukee, Wisconsin), 50 ml of pH 10 buffer solution (Fisher). The resultant trix~lre was stirred at re~ te~ u~ r 8 hol~rs after w~ch i;~
was poured on ice (approximately 100 g) and extracted with diethyl ether. The aqueous layer was then poured into 50 ml of acetone (Fisher) and the resultant, cloudy mixture filtered. The resultant white powder was then run through a sephadex colurnn (Aldrich Chemical Co., Milw~lk~e, Wisconsin) using n-butanol, ethanol, and water (5:4:3 by volume) as eluant to yield a white powder. The yield 1~ was 10.9%.
The degree of substitution of the white powder (tosyl-cyclodextrin) was determined by 13C NMR spectroscopy (DMF-d6) by comparing the ratio of hydroxysubstituted carbons versus tosylated carbons, both at the 6 position. When the 6-position carbon bears a hydroxy group, the NMR peaks for each of the six carbon atoms are given in Table 5.
WO 96/39646 PCT/US~)G1~3.5 Table ~
Carbon Atom NMR Peak (ppm) 101.8 2 72.9 3 72.3 4 81.4 71.9 6 59.8 The presence of the tosyl group shifts the NMR peaks of the S-S position and 6-position carbon atoms to 68.8 and 69.5 ppm, respectively.
The degree of substitution was calculated by integrating the NMR peak for the 6-position tosylated carbon, integrating the NMR
peak for the 6-position hydroxy-substituted carbon, and dividing the former by the latter. The integrations yielded 23.6 and 4.1, respectively, and a degree of substitution of S.9. Thus, the average degree of substitution in this example is about 6.
The tosylated cyclodextrin with the dehydroxy phthaloylglycine 2959 attached was prepared according to the following reaction:
~N--CH2C--O(CH~)*~co CH~
[~'--CH2c--O(CH2)2o~ CH3 To a 250 ml round bottomed flask was added 10.0 g (4-8 mole) of tosylated substituted cyclo~1extTin 20.7g (48 mmol) of ~iol CA 022194~0 1997-11-17 (mercapto dehydrated phthaloylglycine 2959) in 100 ml of DMF.
The reaction mixture was cooled to 0~ C in an ice bath and stirred using a m~gnetic stirrer. To the solution was slowly dropped in 10 ml of ethyl diisopropylamine (Aldrich Chemical Co., Milwaukee, s Wisconsin) in 20 ml of DMF. The reaction was kept at 0~ C for 8 hours with stirring. The reaction ~ ire was extracted with diethyl ether. The aqueous layer was then treated with S00 ml of acetone and the precipitate filtered and washed with acetone. The product was then run on a sephadex column using n-butanol, ethanol, and water (5:4:3 by volume) to yield a white powder. The yield was 16.7 g.
The degree of substitution of the functionalized molecular includant was determined as described above. In this case, the presence of the derivatized ultraviolet radiation transorber shifts the lS NMR peak of the 6-position carbon atom to 63.1. The degree of substitution was calculated by integrating the NMR peak for the 6-position substituted carbon, integrating the NMR peak for the 6-position hydroxy-substituted carbon, and dividing the forrner by the latter. The integrations yielded 67.4 and 11.7, respectively, and a degree of substitution of 5.7. Thus, the average degree of substitution in this example is about 6. The reaction above shows the degree of substitution to be "n". Although n represents the value of substitution on a single cyclodextrin, and therefore, can be from 0 to 24, it is to be understood that the average degree of substitution is about 6.
Example 18 The procedure of Example 17 was repeated, except that the amounts of ~3-cyclodextrin and p-toluenesulfonic acid (Aldrich) were - 30 6.0 g and S.0 g, respectively. In this case, the degree of substitution of the cyclodextrin was found to be about 3.
Example 19 The procedure of Example 17 was repeated, except that the 3s derivatized molecular includant of Example 18 was employed in CA 022194~0 1997-11-17 48 ' place of that from Example 17. The average degree of substitution of the function~ e~ molecular includant was found to be about 3.
F,Y~nP1e 20 This example describes the preparation of a colored composition which includes a mutable colorant and the function~li7~-1 molecular includant from Example 17.
In a 250-ml Erlenmeyer flask cont~inin~ a m~gnetic stirring bar was placed 20.0 g (5.4 mmoles) of the functionalized molecular includant obtained in Example 17 and 100 g of water. The water was heated to 80~C, at which temperature a clear solution was obt~ine-l To the solution was added slowly, with stirring, 3.1 g (6.0 mmoles) of Victoria Pure Blue BO (Aldrich). A precipitate formed which was removed from the hot solution by filtration. The precipitate was washed with 50 ml of water and dried to give 19.1 g (84 percent) of a blue powder, a colored composition consisting of a mutable colorant, Victoria Pure Blue B0, and a molec~ r includant having covalently coupled to it an average of about six ultraviolet radiation transorber molecules per molecular includant molecule.
Example 21 The procedure of Example 20 was repeated, except that the function~li7l--l molecular includant from Example 19 was employed in place of that from Example 17.
Example 22 This example describes mllt~tion or decolorization rates for the compositions of Examples 12 (wherein the ,B--cyclodextrin has dehydrated phthaloyl glycine-2959 from Example 9 covalently bonded thereto), 20 and 21.
In each case, approximately l0 mg of the composition was placed on a steel plate (Q-Panel Company, Cleveland, Ohio). Three drops (about 0.3 ml) of acetonitrile (Burdick & Jackson, Muskegon, Michigan) was placed on top of the composition and the two materials were quickly mixed with a spatula and spread out on the CA 022194~0 1997-11-17 plate as a thin film. Within 5-10 seconds of the addition of the acetonitrile, each plate was exposed to the radiation from a 222-nanometer excimer lamp assembly. The assembly consisted of a bank of four cylindrical lamps having a length of about 30 cm. The lamps were cooled by circ~ tin~; water through a centrally located or inner tube of the lamp and, as a consequence, they operated at a relatively low tempelalule, i.e., about 50~C. The power density at the lamp's outer surface typically was in the range of from about 4 to about 20 joules per square meter (J/m2). However, such range in lo reality merely reflects the capabilities of current excimer lamp power supplies; in the future, higher power densities may be practical. The distance from the lamp to the sample being irr~ te-l was 4.~ cm. The time for each film to become colorless to the eye was measured. The results are sllmm~ri7ed in Table 6.
Table 6 Decolorization Times for Various Compositions Composition ~ecolorization Times (Seconds) Example 20 Example 21 3 4 Example 12 7-8 While the data in Table 6 demonstrate the clear superiority of the colored compositions of the present invention, such data were plotted as degree of substitution versus decolorization time. The plot not only demonstrates the significant improvement of the colored compositions of the present invention when compared with 2s compositions having a degree of substitution less than three, but also indicates that a degree of substitution of about 6 is about optimllm That is, little if any improvement in decolorization time would be achieved with degrees of substitution greater than about 6.
CA 022194~0 1997-11-17 WO 96/39646 PCT/US96tO8887 Example 23 This ex~mple describes the p~ tion of a complex consisting of a mutable colorant and the derivatized molecular includant of Example 17.
s The procedure of Example 20 was repeated, except that the function~li7~-1 molecular includant of Example 17 was replaced with 10 g (4.8 mmoles) of the derivatized molecular includant of F.x~mple 17 and the amount of Victoria Pure Blue BO was reduced to 2.5 g (4.8 mmoles). The yield of washed solid was 10.8 g (86 percent) of a mutable colorant associated with the ~-cyclodextrin having an average of six tosyl groups per molecule of molecular includant.
Example 24 This example describes the preparation of a colored lS composition which includes a mutable colorant and a functionalized molecular includant.
The procedure of preparing a functionalized molecular includant of Example 17 was repe~te-l, except that the tosylated ,13-cyclodextrin was replaced with 10 g (3.8 mmoles) of the complex obtained in F.x~mple 23 and the amount of the derivatized ultraviolet radiation transorber prepared in Example 17 was 11.6 g (27 mmoles). Ihe amount of colored composition obtained was 11.2 g (56 percent). The average degree of substitution was determined as described above, and was found to be 5.9, or about 6.
Example 25 This example describes a method of preparing the following pre-dye of the present invention, wherein X represents a photoinitiator, or wherein X represents a wavelength-specific sensitizer:
N(CH3)2 CH~ 0~30CH2CH20--X
N (CH3)2 The procedure of Examples 1 and 2 is repeated except that the hydroxy ethoxy-dimethyl amino benzophenone of Example 1 is s replaced with X-oxyethoxy-dimethyl arnino benzophenone. The reactions are sllmm~n7~d as follows:
WO 96/39646 PCI~/US96/08887 (CH3)2N ~oCH2CH20X
~C=O + O=C
(CH3)2N N(CH3)2 Mg/HgCI2/RIo.n7~n~.
(cH3)2N N(CH3)2 (CH3)2N ~--C ~ OCH2CH20X
N(CH3)2 (CH3)2N~ ~OCH2CH20X
¢~
N(CH3)2 Example 26 This example describes the preparation of the following pre-S dye.
N(CH3)2 N~C-C:~O(CH ) 0~ ~ ~~~ CH3 CH3 ¢~ 2 2 ~N--CH2Co(CH2)20~3C-C--OH
N(CH3)2 The above pre-dye is prepared as s~lmm~ri7ed below in steps A, B and C.
A.
HO~ p( fi)Acetic Acid \~
I l I O + H2NCH2COH 3 l I I ,NCH2COH
Reflux B.
HO~ICH2COH + Ho(CH2)2o~3c--C~ OH
O R~,n7P-nP.
Toll-nP.nPs~ honic Acid ~O\¢~CH2CO(CHz)20 ~C~ C\&CHO3H
The triarylmethane product prepared in Example 2 is reacted with the reaction product of step B as sllmm~ri7e~1 in reaction step C
below.
S C.
Ho~NCH2co(cH2)2o~3fi) ,CH3 N(CH3)2 (CH3)2N~c~ocH2cH2oH
N(CH3)z Williamson E~er Synthesis Nl(CH3)2 (CH3)2N ~C~3o(cH2)2~NcH2co(cH2)2(~c--C~--OH
N(CH3)2 Example 27 This example describes the preparation of the following pre-dye, wherein X represents a radiation transorber, and wherein R
represents a hydrogen, methyl, or ethyl group.
'. ~
R2N~C--C--X
The procedure of Examples 1 and 2 is repeated except that the hydroxy ethoxy-dimethyl amino benzophenone and bis dimethylaminobenzophenone of Exarnple 1 is replaced with the reactants in the reaction s~lmm~n7ed as follows:
SUBSTITUTE SHEET
R2~
~NR2 R2N~C=O + ~ = C~x Mg/HgCl2/Benzene R2N, ~R2 R~N~C--C--X
~2~Q4 R2N~ --C--X
~' Having thus described the invention, numerous changes and modifications hereof will be readily apparent to those having ordinary skill in the art.
~ a-~5~ r~
Cross-Reference to Related Applications This application is a continuation-in-part application of U.S.
Serial No. 08/649,754, filed May 29, 1996, which is a continuation-in-part application of U.S. Serial No. 08/463,187, filed on June ~, 1995, which are all hereby incorporated by l~r~rt;llce.
Technical Field The present invention relates to novel pre-dyes that are colorless and develop color when exposed to certain wavelengths of electrom~gnstic radiation. The present invention also relates to methods of changing conventional leuco dyes to form colored compositions when exposed to certain wavelengths of electromagnetic radiation.
Background of the Invention It is well known that dyes, in their reduced leuco ~orm, can provide the basis of color image forming systems. The leuco dyes may initially be relatively colorless, but can return to a colored form ' 30 when oxidized, e.g., by nitrate salts in the presence of heat.
Examples of leuco dyes used in color image forming systems include triarylmethanes, xanthenes, styryl dyes, and azine dyes, such as, for example, phen~7in~, phenoxazines, and phenothi~7ines.
It is also known that the leuco form of a given dye may suffer 3s from instability under ambient conditions and can often revert CA 022194~0 1997-11-17 spontaneously to the colored form of the dye. This tendency is increased when photoxidizing agents, for example, trihalogenomethyl compounds which split off halogen radicals upon exposure, are added to obtain an intencification of contrast. A number of stabilizers, for example, sulfur compounds, phenols and other reducing agents have therefore been recommPnt1ed for leuco dye compositions.
Thus, what is needed is a leuco dye that is stable in solution even in the presence of artificial light or sunlight. The ideal leuco dye would be converted to stable colored molecules by exposure to electromagnetic radiation that normally would not be present in ordinary light. In sllmm~ry, it would be extremely desirable to obtain stable leuco derivatives of dyes that could be transformed to a stable colored molecule.
Snmm~ry of the Invention One embodiment of the present invention is a method and composition comprising a novel pre-dye molecule that is colorless and stable to ordinary light. The pre-dye molecule is capable of forming a color when exposed to certain wavelengths of electrom~gnetic radiation.
In particular, the novel pre-dye of the present invention is a dye that is covalently attached to a radiation transorber. The resulting pre-dye molecule is stable in ordinary light but is mutable when exposed to the a~opliate wavelength of electromagnetic radiation. The radiation transorber is desirably composed of a wavelength-specific sensitizer and a photoreactor. When the pre-dye is exposed to the appropriate wavelength of electromagnetic radiation, the pre-dye molecule m~lt~tes and is transformed into the stable colored form of the dye. Accordingly, the present invention also encompasses a method of forming color by exposing the pre-dye to the a~rop.iate wavelength of ultraviolet radiation.
Another embo-lim~nt of the present invention is a conventional leuco dye that is admixed with a radiation transorber, preferably with a molecular includant. When the adllli~LuLe is exposed to the CA 022194~0 1997-11-17 WO 96/39646 PCT/US~6/0~7 ~ro~liate wavelength of electrom~gnPtic radiation, the leuco dye is converted to its colored form.
Yet another emborlim~-nt of the present invention is a method of converting a conventional leuco dye to a colored composition by exposing the leuco dye admixed with a radiation transorber to certain wavelengths of electrom~netic radiation The present invention can be used in im~ing processes including photoim~ing processes, security systems, printing processes, recording processes and the like.
These and other objects, features and advantages of the present invention will become apparent after a review of the following (let~ d description of the disclosed embodiments and the appended claims.
Detailed Description of the Invention The present invention relates, in one aspect, to pre-dyes that are mutable by exposure to narrow band-width radiation to form colored compounds. The present invention more particularly relates to a composition, the pre-dye, comprising a dye molecule which is covalently ~tt~.herl to a radiation transorber. When the dye molecule is covalently ~tt~rh~l to the radiation transorber, the composition is colorless. The pre-dye is mutable when exposed to specific, narrow band-width radiation and mllt~tes to the stable colored form of the dye. Accordingly, the present invention also encompasses a method 2s of forming color by exposing the pre-dye to the appropriate wavelength of ultraviolet radiation.
In another embodiment of the present invention, the composition of the present invention includes an admixture of a conventional leuco dye and a radiation transorber. The leuco dye, in the presence of the radiation transorber, is adapted, upon exposure of the transorber to radiation, preferably ultraviolet radiation, to be mutable to a colored composition. The preferred radiation transorber is adapted to absorb ultraviolet radiation and interact with the leuco dye to effect the irreversible mutation of the molecule to a 3s colored composition.
CA 022194~0 1997-11-17 WO 96/39646 PCI~/US96/08887 Yet another embo~limPnt of the present invention is a method of converting a conventional leuco dye to a colored composition by exposing the leuco dye a-lmixed with a radiation transorber to certain wavelengths of electrom~gnPtic radiation After definitions of various terms used herein, the pre-dye of the present invention and methods of developing color using the same are described in detail, followed by a description of the leuco dye/radiation transorber admixture and methods of developing color using the same.
Definitions As used herein, the term "dye" is meant to include, without limitation, any m~tPri~l which typically will be an organic rn~tçri~l, such as an organic colorant or pi~;mP~t Desirably, the dye will be substantially transparent to, that is, will not significantly interact with, the ultraviolet radiation to which it is exposed. The term is meant to include a single m~teri~l or a mixture of two or more m~teri~
The term "pre-dye" or "pre-dye molecule" as used herein m~n.~ a dye molecule that is covalently attached to a radiation transorber so that the composition is colorless. Upon irradiation with the appropriate wavelength of electromagnetic radiation, the composition is capable of ft~rming a colored composition.
The term "leuco dye" refers to the leuco form of a dye, or 2s colorless form, and is the reduced form of the dye having one or two hydrogen atoms, the removal of which, together with an additional electron in certain cases, produces the colored dye.
As used herein, the term "irreversible" means that the dye will not revert to its original color when it no longer is exposed to ultraviolet radiation.
The term "composition" and such variations as "colored composition" are used herein to mean a dye, and a radiation transorber. When reference is being made to a colored composition which is adapted for a specific application, the term "composition-CA 022194~0 1997-11-17 WO 96/39646 PCT/US96/0~87 based" is used as a modifier to indicate that the material includes a dye, a radiation transorber and, optionally, a molec~ r incl~ nt The term "molecular incl~ nt," as used herein, is intended to mean any substance having a chemical structure which ~lefinPs at least one cavity. That is, the molecular includant is a cavity-cont~inin~
structure. As used herein, the term "cavity" is meant to include any opening or space of a size sufficient to accept at least a portion of one or both of the dye and the radiation transorber. The molecular includant can also include a cavity-cont~inin~ molecule to which the radiation transorber is optionally covalently attached. A description of the method of preparing molecular includants covalently ~tt~'h~d to radiation transorbers, and their association with colorants, is described in Examples 6-24, and in copending patent application serial no. 08/461,372, filed June 5, 1995, which is incorporated herein by reference.
The term "functionalized molecular includant" is used herein to mean a molecular includant to which one or more molecules of an ultraviolet radiation transorber are covalently coupled to each molecule of the molecular includant. The term "degree of substitution" is used herein to refer to the number of these molecules or leaving groups (defined below) which are covalently coupled to each molecule of the molecular inch~ nt The term "derivatized molecular includant" is used herein to mean a molecular includant having more than two leaving groups covalently coupled to each molecule of molecular includant. The term "leaving group" is used herein to mean any leaving group capable of participating in a bimolecular nucleophilic substitution reaction.
The term "ultraviolet radiation" is used herein to mean electromagnetic radiation having wavelengths in the range of from about 4 to about 400 nanometers. The especially desirable ultraviolet radiation range for the present invention is between approximately 100 to 375 nanometers. Thus, the term includes the regions commonly referred to as ultraviolet and vacuum ultraviolet. The wavelength ranges typically assigned to these two regions are from CA 022194~0 1997-11-17 about 180 to about 400 nanometers and from about 100 to about 180 nanometers, respectively.
The term "mutable," with reference to the pre-dye or the leuco dye/radiation transorber mixture is used to mean that the absorption s maximum of the dye is capable of being mutated or changed by exposure to radiation, preferably ultraviolet radiation, when in the presence of the radiation transorber so that the absorption ma~iml-m is shifted to the visible region. In general, it is only necessary that such absorption maximllm be mllt~te~l to an absorption ma~imllm which is different from that of the pre-dye prior to exposure to the ultraviolet radiation, and that the mutation be irreversible. In other words, the dye can mllt~te from colorless to a color.
The term "compound" is intended to include a single m~teri~l or a ll~ib~Lule of two or more materials. If two or more m~teri~l.c OEe lS employed, it is not nPcess~ry that all of them absorb radiation of the same wavelength. As discussed more fully below, a radiation transorber is comprised of a photoreactor and a wavelength selective sen~iti7f~r~
The term "radiation transorber" is used herein to mean any m~teri~l which is adapted to absorb radiation at a specific wavelength and interact with the dye to affect the mllt~tion of the dye. In some embo-l;meIlts, the radiation transorber may be an organic compound.
A description of the synthesis of the radiation transorber is described in Examples 6-8, and 13, and in copending patent application serial 2s no. 08/461,372, filed June 5, l99S, which is incorporated herein by reference.
Pre-Dye Molecule One embodiment of the present invention is a pre-dye molecule that is mutable by exposure to narrow band-width radiation to form a colored compounds. The present invention more particularly relates to a composition, the pre-dye molecule or "pre-dye", comprising a dye molecule which is covalently attached to a radiation transorber. When the dye molecule is covalently attached 3s to the radiation transorber, the composition is colorless. The pre-CA 022194~0 1997-11-17 dye is mutable when exposed to specific, narrow band-width radiation and mutates to the stable colored form of the dye.
The present invention includes unique compounds, namely, radiation transorbers, that are capable of absorbing narrow wavelength ultraviolet radiation. The compounds are synthesized by combining a wavelength-selective sensitizer and a photoreactor.
Generally, photoreactors do not efficiently absorb high energy radiation. However, when a photoreactor is combined with a wavelength-selective sensitizer, the resulting compound is a wavelength specific compound that efficiently absorbs a very narrow spectrum of radiation. In this compound the wavelength-specific sensitizer generally absorbs radiation having a specific wavelength, and therefore a specific amount of energy, and transfers the energy to the photoreactor. Desirably, the wavelength-selective sensitizer is covalently coupled to the photoreactor.
Accor~ngly, th~ radiati~n transorber that is attached to the dye molecule is capable of absorbing radiation and interacting with the dye molecule to effect a mllt~tion of the pre-dye to form a colored compound. The radiation transorber may be any material which is adapted to absorb radiation and interact with the dye to effect the mutation of the dye. It is desirable that the mutation of the pre-dye be irreversible. In the desired embodiment, the radiation transorber is covalently attached to the dye molecule thereby rendering the dye molecule colorless.
By way of example, the wavelength-selective sensitizer may be, but is not limited to, phthaloylglycine or 4-(4-hydroxy-phenyl)-2-butanone. These wavelength-specific sensitizers are illustrated below:
Phthaloylglycine [~N {~H2--C--OH
~ = = ~
CA 022194~0 1997-11-17 WO 96/39646 PCT/US9CI~ 9~7 4-(4-Hydroxy phenyl) butan-2-one CH3--C--CH2~H2~30H
The photoreactor may be, but is not limited to, 1-(4-(2-hydroxyethoxy)phenyl)-2-hydroxy-2-methylpropan-1-one (Darocur-2959) or l-hydroxycyclohexane phenyl ketone (Irgacure 184).
These reactive species-generating photoinitiators are illustrated below:
HO--(CH2)2--~~ CH
Irgacure 184 (l-hydroxycyclohexane phenyl ketone) C~OHJ~
It is to be understood that the above n~m~l sensitizers and photoreactors are named in their unbonded form. For example, where the photoreactor l-hydroxycyclohexane phenyl ketone is covalently bonded to a sensitizer via its hydroxy group, the photoreactor moiety may be denoted as cyclohexyl-phenyl ketone ester. Where the sensitizer 4-(4-hydroxyphenyl)-2-butanone is 2s covalently bonded to a photoreactor via its hydroxy group, the sensitizer moiety may be denoted as 4-(4-oxyphenyl)-2-butanone.
Similarly, where the sensitizer phthaloylglycine is covalently bonded to a photoreactor via its hydroxy group, the sensitizer moiety may be denoted as phthaloylglycyl. When the sensitizer is covalently bonded to the photoreactor, these sensitizers and photoreactors may be ref~lled to in their unbonded form for simplicity.
By way of example, the radiation transorber may be 2-(p-(2-methyllactoyl)phenoxy)ethyl 1,3-dioxo-2-isoindoline-acetate s having the formula o ¢C~N--CH~ O(CH ) ~~3e~ ~CH3 phthaloylglycyl-cyclohexylphenyl ketone ester having the formula ~N--CH2--C--0~
~, 4-(4-oxyphenyl)-2-butanone- 1 -(4-(2-oxyethoxy)phenyl)-2-hydroxy-1S 2-methyl-propan- 1 -one (or 2-hydroxy-2-methyl-4'-(2-(p-(3-oxobutyl)phenoxy)ethoxy)-propiophenone) having the formula CH3--C--CH2CH2~O--CH2CH2--O~C--I OH
or CA 022194~0 1997-11-17 WO 96/39646 PCT/US96~ 7 4-(4-oxyphenyl)-2-butanonecyclohexyl-phenyl ketone (or 4-(p-((4-benzoylcyclohexyl)oxy)phenyl)-2-butanone) having the formula CH3~ ~H2CH2~30~
~0 Examples 6-8, and 13 describe methods of preparing the above radiation transorbers. It is to be understood that other sensitizers, photoreactors, and radiation transorbers than those specifically listed above may be used in the present invention.
Accordingly, the following formula represents a pre-dye wherein the dye molecule is a leuco form of crystal violet (N-(4-(Bis(4-(~limt-~hylamino)phenyl)methylen-2,5-cyclohexa-dien- l-ylidene)-N-methylmeth~n~minium chloride) covalently bonded to X, wherein X represents a radiation transorber, or wherein X represents a wavelength-specific sensitizer covalently bonded thereto, wherein the oxyethoxyphenyl group functions as a photoreactor.
,D~H3)2 N~--C~OCH2CH2O--X
N(CH3)2 A method of preparing the above pre-dye is described in Example 25.
_ WO 96/39646 PCI'/US96/08887 By way of example, the pre-dye may be, but is not limited to, the following formulas: =
IN(CH3)2 (CH3)2N ~ ~c O OCH2CH20CCH2--N~
N(CH3)2 N(CH3)2 C~¢l ~ ~N-cH2c 0 N(cH3)2 WO 96/39646 PCI'/US96/08887 ~H3)2 lC~3~(C"2)20C''2C(C"2)2 \=/ O(Cn2)20~3C--v~vn CH3 ¢~
N(CH3~2 N(CH3)2 1 ~3ll~o(cH2)2ocH2c(cH2)2~o~
CH3 ,J~, C=O
N(CH3)2 or ~H3)2 C~ 3 0~CHz)zO~ N--CH ~CO(CHz)zO~ lOc_c CHOJH
O
N(CH3)2 A method of preparing the following pre-dye is described in Example 26.
WO 96t39646 PCr/US96/08887 N(CH3)2 3o(cH2)2o~N--cH28o(cHz)2o~loc--c~cHH~H
N(CHs)z A desired pre-dye has the following formula:
N(CH3)2 (CH3)2N{~--?~ c OCH2CH20CCH2--N~X3 N(CH3)2 This particular structure shows the radiation transorber, 2-(p-(2-methyllactoyl)phenoxy)ethyl 1,3-dioxo-2-isoindolineacetate, attached to crystal violet (N-(4-(Bis(4-(dimethylamino)-phenyl)methylen-2,5-cyclohexedien- 1 -ylidene)-N-methyl-meth~n~minium chloride). Examples 1-3 describe how to prepare the above pre-dye molecule.
It is to be understood that the disclosed formulas are merely an example of the pre-dye concept that is considered part of the present invention and that other dyes can be substituted for the crystal violet and other radiation transorbers can be employed in substitution of the above radiation transorbers.
For example, the following are other pre-dyes of the present invention, wherein X represents a radiation transorber, and wherein R represents a hydrogen, methyl, or ethyl group.
WO 96t39646 PCT/US96~33 R2N~--C--X
~1 ~3~
F.x~mrle 27 describes a method for preparing the following lo pre-dye.
PCT/US96/Og'?fl7 R2N ~C--C--X
~C
Additional examples of other pre-dyes of the present invention include the following, wherein R represents an alkyl or aryl group.
Nl (CH3)2 (CH3)2N~ H CH3 N(cH3)2 CA 022l9450 l997-ll-l7 WO 96/39646 PCT/US9G/~.~3~ /
N(CH3)2 (CH3)2N ~--C--C=CI--R
N(cH3)2 N(cH3)2 (CH3)ZN~c~ 3CH2--~3 N(CH3)2 or CA 022194~0 1997-11-17 ~(CH3)2 ~ 1 11 (CE~3)~N--~ ~8~3 N(CH3)2 The present invention also relates to a method of forming a colored composition. The method comprises irradiating a composition containing a pre-dye. The pre-dye is a molecule comprising a dye molecule covalently attached to a radiation transorber. When the dye molecule is covalently ~tt~rh~-d to the radiation transorber, the composition is colorless. The method comprises exposing the pre-dye to ultraviolet radiation at a dosage lo level sufficient to mllt~te the dye. Example 4 further illustrates the method of forming a colored composition lltili7in~ the pre-dye of the present invention.
The pre-dye of the present invention can be irradiated with radiation having a wavelength of between about 4 to about 1,000 nanometers depen~lin~ upon the radiation transorber that is present in the composition. Thus, the radiation may be ultraviolet radiation, including near ultraviolet and far or vacuum ultraviolet radiation;
visible radiation; and near infrared radiation. Desirably, the pre-dye is irradiated with radiation having a wavelength of from about 4 to about 700 nanometers. More desirably, the pre-dye is irradiated with ultraviolet radiation having a wavelength of from about 4 to about 400 nanometers. It is more desirable that the radiation have a wavelength of between about 100 and 375 nanometers.
The present invention also relates to a substrate having an 2s image thereon that is formed by the pre-dye molecule of the present invention.
CA 022l94~0 l997-ll-l7 WO 96/39646 PCT/US~)6/0~7 Leuco Dye/~n~i~7tiQn Transorber Admucture In another embodiment of the present invention, the composition of the present invention includes an admixture of a conventional leuco dye and a radiation transorber. The leuco dye, in the presence of the radiation transorber, is adapted, upon exposure of the transorber to radiation, ~leferably ultraviolet radiation, to be mutable to a colored composition. The preferred radiation transorber is adapted to absorb ultraviolet radiation and interact with the leuco dye to effect the illevelsible mutation of the molecule to a colored composition.
The radiation transorbers that may be admixed with a leuco dye in the present invention are described above.
Leuco dyes that can be used in the present invention include, but are not limited to, aminotriarylmethanes, aminoxanthenes, aminothioxanthenes, amino-9, 1 0-dihydroacridines, ~minopheno~c~7.inl~s, aminophenothi~7inçs~ ~minodihydroph~n~7in~s, aminodiphenylmPth~nes, leuco in~l~mines, aminohydrocinn~mic acids (cyanoethanes, leucomethines), hydrazines, leuco indigoid dyes, amino-2,3-dihydroanthraquinones, phen~thyl~nilin~-s, 10-acyl-aminodihydrophen~7ines, 10-acyl-aminophenothi~7inPs, 10-acyl-aminophenoxazines and aminotriarylm~th~nes wherein the m~th~ne hydrogen has been replaced by an alkylthio, benzylthio, 2-phenylhydrazino, or alkoxycarbonyl group. The generally 2s preferred class of leuco dyes is the aminotriarylmethane class and derivatives thereof. The aminotriarylmethane dyes, as well as the other classes of dyes, are reviewed in Abrahart, E.N., Dyes and their Intermediates, Chemical Publishing Co., Inc., (1977) which is incorporated herein by lefelellce. The aminotriarylmethanes are reviewed at page 151 of the Abrahart reference. A desirable leuco dye is an aminotriarylmethane dye.
The present invention also includes forming a colored molecule from a leuco dye by admixing the leuco dye with a radiation transorber, and irr~ ting the adrnixture with certain wavelengths of electrom~gnçtic radiation.
CA 022194~0 1997-11-17 The leuco dye composition of the present invention can be irradiated with radiation having a wavelength of between about 4 to about 1,000 nanometers depending upon the radiation transorber that is present in the composition. Thus, the radiation may be ultraviolet s raA;ation, in~ iR~ near ultr~i~et a~d ~ cu~m ultraviolet radiation; visible radiation; and near infrared radiation. Desirably, the composition is irr~ ted with radiation having a wavelength of from about 4 to about 700 nanometers. More desirably, the composition of the present invention is irradiated with ultraviolet radiation having a wavelength of from about 4 to about 400 nanometers. It is more desirable that the radiation have a wavelength of between about 100 to 375 nanometers.
In another embodiment, the pre-dye composition is applied to a substrate before being irr~ ted with ultraviolet radiation. The present invention is also related to a substrate having an image thereon that is formed by the leuco dye composition of the present invention. It is desirable that the ....~ted dye is stable.
Although the leuco dye and the r~A~i~tion transorber have been described as separate compounds, they can be part of the same molecule, in which case the single molecule is desi~n~teA. a pre-dye.
For example, the dye and the radiation transorber can be covalently coupled to each other, either directly, or indirectly through a relatively small molecule or spacer. ~ltern~tively, the dye and radiation transorber can be covalently coupled to a large molecule, 2s such as an oligomer or a polymer. Further, the dye and radiation transorber may be associated with a large molecule by van der Waals forces, and hydrogen bonding, among other means. Other variations will be readily apparent to those having ordinary skill in the art.
The pre-dye and the leuco dye/radiation transorber admixtures of the present invention may optionally contain a molecular includant having a chemical structure which Aefin~s at least one cavity. Thus, the cavity in the molecular includant can be a tunnel through the molecular includant or a cave-like space or a dented-in space in the molecular includant. The cavity can be isolated or independent, or 3s connected to one or more other cavities.
CA 022194~0 1997-11-17 WO 96/39646 PCI'/US96/08887 The molecular includant can be inorganic or organic in nature.
In certain embo(lim~nts, the chemical structure of the molecular includant is adapted to form a molecular inclusion complex. The molecular includants include, but are not limited to, clathrates, zeolites, and cyclodç~trin~. Examples of cyclodextrins include, but are not limited to, a-cyclodextrin, ~-cyclofl~ctrin~ ~f-cyclodextrin, hydroxypropyl 13-cyclodextrin, hydroxyethyl ,~-cyclodextrin, sulfated ~-cyclodextrin, hydroxyethyl a cyclodextrin, carboxymethyle a cyclodextrin, carboxymethyl ~-cyclodextrin, carboxymethyl ~ cyclodextrin, octyl succinated a cyclodextrin, octyl succinated ~-cyclodextrin, octyl succinated ~ cyclodextrin and slllf~t~d ,13 and ~-cyclodextrin (American Maize-Products Company, ~mmond, Indiana).
The desired molecular includant is a cyclodextrin. More par~icularly, in some embo-limPnts, the desired molecular includant is an a-cyclodextrin. In other embo-lim~ntc, the desired molecular includant is a ~-cyclodextrin. In yet other embo~iim~nt~7 the desired molecular includant is ry-cyclodextrin.
In those embodiments where the leuco dye molecule and the radiation transorber are adrnixed, each of the leuco dye and radiation transorber is optionally associated with one or more molecular includants. In some emborlimPnt~, the leuco dye is at least partially included within a cavity of the molçc-ll~r inclu-l~nt and the radiation transorber is associated with the molecular includant outside of the cavity. In some embo~lim~nt~7 the radiation transorber is covalently coupled to the outside of the molecular includant.
For example, the leuco dye and/or the radiation transorber can be m~int~ined in close proximity to the molecular includant by hydrogen bonding, van der Waals forces, or the like. The term "associated", in its broadest sense, means that the leuco dye and the radiation transorber are at least in close proximity to the molecular includant. Alternatively, either or both of the leuco dye and the radiation transorber can be covalently bonded to the molecular includant. In certain embodiments, the leuco dye will be associated with the molecular includant by means of hydrogen bonding and/or CA 022194~0 1997-11-17 WO 96/39646 PCT/US!)6/08887 van der Waals forces or the like, while the radiation transorber is covalently bonded to the molec~ r incl~ nt In other embo-liment~, the leuco dye is at least partially included within the cavity of the molecular includant, and the radiation transorber is located outside of the cavity of the molecular includant. It is to be understood that one or more radiation transorbers may be associated with one molecular includant, one or more leuco dyes may be associated with one molecular includant, or one or more of both may be associated with one molecular includant. It is also to be understood that one or more pre-dyes may be associated with a molecular includant, or one pre-dye may be associated with more than one molecular includant.
In several embodiments, the radiation transorber molecule, the wavelength-selective sensitizer, or the photoreactor may be associated with a molecular includant. It is to be noted that the number of such molecules can be between approximately 1 and approY~tr.a~.ely 21 ~oleeul~ ~er ~l~ar in~ Of ~se, ifi certain situations, there can be more than 21 molecules per molecular includant molecule. Desirably, there are more than three of such molecules per molec~ r includant.
The degree of substitution of the functionalized molecular includant may be in a range of from 1 to approximately 21. As another example, the degree of substitution may be in a range of from 3 to about 10. As a further example, the degree of substitution may be in a range of from about 4 to about 9.
The leuco dye may be associated with the functionalized molecular includant. The term "associated" in its broadest sense means that the leuco dye is at least in close proximity to the function~li7e-1 molecular includant. For example, the leuco dye may be m~int~ined in close proximity to the functionalized molecular includant by hydrogen bonding, van der Waals forces, or the like.
Alternatively, the leuco dye may be covalently bonded to the ~ functionalized molecular includant, although this normally is neither desired nor necessary. As a further example, the leuco dye may be at least partially included within the cavity of the functionalized molecular includant.
CA 022194~0 1997-11-17 The ex~mples below disclose methods of ~repaLing and associ~ting colorants and ultraviolet radiation transorbers to ~-cyclo~e~trin~. For illustrative purposes only, F.~mples 6, 7, 11, and 12 disclose one or more methods of preparing and associating S colorants and ultraviolet radiation transorbers to cyclodextrins.
In those embodiments of the present invention in which the ultraviolet radiation transorber is covalently coupled to the molecular includant, the efficiency of energy transfer from the ultraviolet radiation transorber to the leuco dye is, at least in part, a function of the number of ultraviolet radiation transorber molecules which are ~tt~f hPd to the molecular includant.
Accordingly, the present invention also relates to a composition which includes a leuco dye and a functionalized molecular incl~ nt For illustrative purposes only, Examples 14 1S through 21, and 23 through 24 disclose other methods of preparing and associating colorants and ultraviolet radiation transorbers to cyclodextrins, wherein more than two molecules of the ultraviolet radiation transorber are covalently coupled to each molecule of the molecular includant.
The present invention also provides a method of making a functionalized molecular includant. The method of m~king a functionalized molecular includant involves the steps of providing a derivatized ultraviolet radiation transorber having a nucleophilic group, providing a derivatized molecular includant having more than 2s two leaving groups per molecule, and reacting the derivatized ultraviolet radiation transorber with the derivatized molecular includant under conditions sufficient to result in the covalent coupling of an average of more than two ultraviolet radiation transorber molecules to each molecular includant molecule. By way of example, the derivatized ultraviolet radiation transorber may be 2-[p-(2-methyl-2-mercaptomethylpropionyl)phenoxy~ethyl 1,3-dioxo-2-isoindoline-acetate. As another example, the derivatized ultraviolet radiation transorber may be 2-mercaptomethyl-2-methyl-4'-[2-[p-(3-oxobutyl)phenoxy]ethoxy]propiophenone.
CA 022l94~0 l997-ll-l7 In general, the derivatized ultraviolet radiation transorber and the derivatized molecular includant are selected to cause the covalent coupling of the ultraviolet radiation transorber to the molecular includant by me7lns of a bimolecular nucleophilic substitution reaction. Consequently, the choice of the nucleophilic group and the leaving groups and the preparation of the derivatized ultraviolet radiation transorber and derivatized molecular includant, respectively, may be readily accomplished by those having ordinary skill in the art without the need for undue experimentation.
The nucleophilic group of the derivatized ultraviolet radiation transorber may be any nucleophilic group capable of participating in a bimolec~ r nucleophilic substitution reaction, provided, of course, that the reaction results in the covalent coupling of more than two molecules of the ultraviolet radiation transorber to the molecular incl~ nt The nucleophilic group generally will be a Lewis base, i.e., any group having an unshared pair of electrons. The group may be neutral or negatively charged. Examples of nucleophilic groups include, by way of illustration only, aliphatic hydroxy, aromatic hydroxy, alkoxides, carboxy, carboxylate, amino, and mercapto.
Similarly, the leaving group of the derivatized molecular includant may be any leaving group capable of participating in a bimolecular nucleophilic substitution reaction, again provided that the reaction results in the covalent coupling of more than two molecules of the ultraviolet radiation transorber to the molecular includant. Fx~mples of leaving groups include, also by way of illustration only, p-toluenesulfonates (tosylates), p-bromobenzenesulfonates (brosylates), p-nitrobenzenesulfonates (nosylates), methanesulfonates (mesylates), oxonium ions, alkyl perchlorates, ammonioalkane sulfonate esters (betylates), alkyl fluorosulfonates, trifluoromethanesulfonates (triflates), nonafluorobutanesulfonates (nonaflates), and 2,2,2-trifluoroethanesulfonates (tresylates).
The reaction of the derivatized ultraviolet radiation transorber with the derivatized molecular includant is carried out in solution.
The choice of solvent depends upon the solubilities of the two CA 022194~0 1997~ 17 SUBSTrruTE SHEET
.... ..... .. . - . .. .
derivatized species. As a practical matter, a particularly useful solvent is N,N-dimethylforrnamide (DMF).
The reaction conditions, such as temperature, reaction time, and the like generally are matters of choice based upon the natures of the nucleophilic and leaving groups. Elevated temperatures usually are not required. For example, the reaction temperature may be in a range of from about 0~C to around ambient temperature, i.e., to 20~-25~C.
The preparation of the functionalized molecular includant as described above generally is carried out in the absence of the colorant or leuco dye. However, the leuco dye may be associated with the derivatized molecular includant before reacting the derivatized ultraviolet radiation transorber with the derivatized moiecular includant, particularly if a degree of substitution greater than about three is desired. When the degree of substitution is about three, it is believed that the association of the leuco dye with the functionalized molecular includant still may permit the leuco dye to be at least partially included in a cavity of the functionalized molecular includant. At higher degrees of substitution, such as about six, steric hindrance may partially or completely prevent the leuco dye from being at least partially included in a cavity of the functionalized molecular includant. Consequently, the leuco dye may be associated with the derivatized molecular includant which 2s normally will exhibit little, if any, steric hindrance. In this instance, the leuco dye will be at least partially included in a cavity of the derivatized molecular includant. The above-described bimolecular nucleophilic substitution reaction then may be carried out to give a composition of the present invention in which a leuco dye is at least partially included in a cavity of the functionalized mol~ular ir~cllx~rlt.
Example 5 describes a method of producing color by irr~ ing a leuco dye admixed with a radiation transorber attached to a ~-cyclodextrin.
The present invention is further described by the examples which follow.
..
~, SUBSTITUTE ~HEET . . ~ , ,"., In the examples, all parts are parts by weight unless stated otherwise.
~mrle I
Preparation of a pinacol type starting material.
The starting material for the pre-dye molecule which will have a blue color when irradiated is prepared according to the following reaction:
(cH3)2N O--CH2CH2,0H
C=O + O=C ~ Mg (C 13)2N 1 HgC12N(CH3)2 (CH3)~N N(CH3)2 OH OH '~ OCH2CH2OH
In a S00 ml round bottom 3-necked flask fitted with a magnetic stir bar, condensor, addition funnel was placed 10 g (0.037 mole) bis dimethylaminobenzophenone (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin), 1 g hydroxy ethoxy-dimethyl amino benzophenone (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin) and 0.75 g magnesium shavings (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin). 200 ml of anhydrous benzene was poured into the reaction mixture and was heated to 50~C and 0.84 g of mercury chloride in 20 ml benzene was slowly added ~~)~o S~
WO 96/39646 PCT/US9G,'1~9 9 ~7 over 20 minutes. The reaction was initi~te~l by ~ ling a small crystal of iodine to the flask. The reaction mixture was heated for 30 minutes. The organic layer was separated, dried and the solvent removed under reduced pressure to yield a yellow solid. The product s was run on a short silica column with 50% ethyl ~cet~t~ in hexane as solvent.
Mass Spec: 538 (m+-OH), 521, 480, 252 ~mple 2 The product from Fx~mple 1 was treated according to the following reaction:
(cH3)2N N(CH3)2 (CH3)2N-- --C_C~ }OCH2CH20H
N(CH3)2 ~0 (CH3)2N CbC O OCH2CH20H
N(CH3)2 1S To a 250 ml round bottomed flask was added 5.0 g (9 mmole) of the diol from Example 1, and a magnetic stir bar. 50 ml of 50%
concentrated sulfuric acid in water was added and the reaction mixtl-re stirred in an ice bath for 1 hour. The pH of the reaction WO96/39646 PCr/US96 mixture was then brought up to approximately 7.0 by addition of sodium hydroxide. The precipitate was filtered and dried under v~c~ m for 2 hours. The yield was 4.2 g (88%).
Mass Spec: 537 (m+), 520, 448, 433 F,x~mple 3 The product from Example 2 was subjected to the following reaction:
N(CH3)2 (CH3)2N~C~-C~30CH ~CH20H + HOzCClI2--N~
N(CH3)2 Rçn7Pn~-Tosyl Acid ~(CH3)2 (cH3)2N~co{~ocHzcH2occH2-N~3 N(cH3)2 In a 250 ml round bottom flask fitted with a m~gnetic stir bar, Dean & Stark adaptor and condensor was added 4.0 g (7.6 mmole) ketone from Example 2, 1.5 g phthaloylglycine (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin), O.lgp-toluenesulphuric acid (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin) and 100 ml of anhydrous benzene (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin). The reaction mixture was heated at reflux for 8 hours after which time 0.3 ml of water had been collected in the adaptor. Removal of the solvent under reduced pressure gave 5.0 g of product.
t CA 022194~0 1997-11-17 SUBSTlTUTE SHEl~T
28 ~ ~ ..................... ..
Example 4 0.2 g of the product from Example 3 compound was dissolved in 5 ml of acetonitrile (Fisher Scientific, Pittsburgh, Pennsylvania). 3 drops of the mixture was placed on a metal plate (Q-panel) and spread out with the aid of a spatula. The plate was then exposed to 222 nm excimer radiation at 12.19 m/minute (40 ft/minute) on the conveyer. A deep blue color developed on radiation.
Four drops were placed on a sheet of white paper (Neenah bond) and allowed to spread out. The moist sheet was then exposed to 222 nm excimer radiation. The moist area turned a deep blue in color.
Example 5 A leuco dye (leuco crystal violet) (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin) was mixed with a composition comprising a radiation transorber attached to a ,13-cyclodextrin represented by the following formula:
~-cyclodextrin ~(~2CH2 ~ C~2~N--CH,C--o(C~2).o~3~ C~ ]
The synthesis of the radiation transorber attached to a ,13-cyclodextrin is described in Examples 8-11, and in copending U.S. Patent Application Serial No. 08/461,372 filed on June 5, 1995 and incorporated herein by reference. O.lg leuco crystal violet dye and 0.2 g a radiation transorber attached to a ,(3-cyclodextrin was mixed in 5 ml acetonitrile (Fisher Scientific, Pittsburgh, Pennsylvania). The colorless solution was placed on a metal plate (Q-panel) and spread out with a spatula (approximately 5 drops of solution). The plate was passed under the 222 nm excimer lamp. (10.67 m/minute (35 ft/minute) on the conveyer) after which the solution had turned a deep blue in color. This was repeated by putting 3 drops onto paper (Neenah Bond) and oSt~E
CA 022194~0 1997-11-17 29.
spreading it with a spatula. Passing the moist paper under a 222 nm dielectric barrier discharge excimer lamp (Haraus Noblelight AG, Hanau, Gerrnany) developed a blue color. Leuco dye by itself did not develop any color on irradiation with 222 nm.
s ~mrle 6 This example describes the preparation of a b-cyclodextrin molecular includant having (1) an ultraviolet radiation transorber covalently bonded to the cyclodextrin outside of the cavity of the cyclodextrin, and (2) a colorant associated with the cyclodextrin by means of hydrogen bonds and/or van der Waals forces.
A. Friedel-Crafts Acylation of Transorber A 250-ml, three-necked, round-bottomed reaction flask was fitted with a contlçn~er and a pressure-eqll~li7ing addition funnel equipped with a nitrogen inlet tube. A magnetic stirring bar was placed in the flask. While being flushed with nitrogen, the flask was charged with 10 g (0.05 mole) of l-hydroxycyclohexyl phenyl ketone (IRGACURE 184, Ciba-Geigy Corporation, Hawthorne, New York), 100 ml of anhydrous tetrahydofuran (Aldrich Chemical Company, Inc., Milw~lk~e, Wisconsin), and 5 g (0.05 mole) of succinic anhydride (Aldrich Chemical Co., Milwaukee, WI). To the continuously stirred contents of the flask then was added 6.7 g of anhydrous aluminum chloride (Aldrich Chemical Co., Milw~llkt-e, Wisconsin). The resulting reaction llli~l~e was m~int~ined at about 0~C in an ice bath for about one hour, after which the ll.~Lule was allowed to warm to ambient temperature for two hours. The reaction mixture then was poured into a mixture of 500 ml of ice water and 100 ml of diethyl ether. The ether layer was removed after the addition of a small amount of sodium chloride to the aqueous phase to aid phase separation. The ether layer was dried over anhydrous m~gn~sium sulfate. The ether was removed under reduced pressure, leaving 12.7 g (87 percent) of a white crystalline powder. The m~teri~l was shown to be l-hydroxycyclohexyl 4-(2-CA 022194~0 1997-11-17 carboxyethyl)carbonylphenyl ketone by nuclear m~gnetic resonance analysis.
B. Preparation of Acylated Transorber Acid Chloride A 250-ml round-bottomed flask fitted with a condenser was charged with 12.0 g of l-hydroxycyclohexyl 4-(2-carboxyethyl)carbonylphenyl ketone (0.04 mole), 5.95 g (0.05 mole) of thionyl chloride (Aldrich Chemical Co., Milwaukee, Wisconsin), and 50 ml of diethyl ether. The resulting reaction mixture was stirred at 30~C for 30 minutes, after which time the solvent was removed under reduced pressure. The residue, a white solid, was maintained at 0.01 Torr for 30 minlltes to remove residual solvent and excess thionyl chloride, leaving 12.1 g (94 percent) of 1-hydroxycyclohexyl 4-(2-chloroformylethyl)carbonylphenyl ketone.
C. Covalent Bonding of Acylated Transorber to Cyclodextrin A 250-ml, three-necked, round-bottomed reaction flask containing a m~gnetic stirring bar and fitted with a thermometer, condenser, and pressure-eq~l~li7ing addition funnel equipped with a nitrogen inlet tube was charged with 10 g (9.8 mmole) of ~-cyclodextrin (American Maize-Products Company, Hammond, Indiana), 31.6 g (98 mmoles) of l-hydroxycyclohexyl 4-(2-chloroformylethyl)carbonylphenyl ketone, and 100 ml of N,N-~lim~thylforrn~mide while being continuously flushed with nitrogen.
The reaction mixture was he~tP~ to 50~C and 0.5 rnl of triethyl~min~
added. The reaction ~ u~e was m~int~in~rl at 50~C for an hour and allowed to cool to ambient temperature. In this preparation, no ~ttempt was made to isolate the product, a ~-cyclodextrin to which an ultraviolet radiation transorber had been covalently coupled (referred to hereinafter for convenience as ~-cyclodextrin-transorber).
The foregoing procedure was repeated to isolate the product of the reaction. At the conclusion of the procedure as described, the reaction mixture was concentrated in a rotary evaporator to roughly 10 percent of the original volume. The residue was poured into ice CA 022194~0 1997-11-17 water to which sodium chloride then was added to force the product out of solution. The resulting precipitate was isolated by filtration and washed with diethyl ether. The solid was dried under reduced pressure to give 24.8 g of a white powder. In a third ~e~a~dtion, the residue rem~ining in the rotary evaporator was placed on top of an approximately 7.5-cm column cont~ining about 15 g of silica gel.
The residue was eluted with N,N-~lim~thylform~mide, with the eluant being monitored by me~n.s of Wh~tm~n(~) Flexible-Backed TLC
Plates (Catalog No. 05-713-161, Fisher Scientific, Pittsburgh, Pennsylvania). The eluted product was isolated by evaporating the solvent. The structure of the product was verified by nuclear m~gnetic resonance analysis.
D. Association of Colorant with Cyclodextrin-Transorber-Preparation of Colored Composition To a solution of 10 g (estim~tt~l to be about 3.6 mmole) of ~-cyclodextrin-transorber in 150 ml of N,N-dimethylform~mide in a 250-ml round-bottomed flask was added at ambient temperature 1.2 g (3.6 mmole) of Malachite Green oxalate (Aldrich Chemical Company, Inc., Milw~llk~e7 Wisconsin), lefelled to hereinafter as Colorant A for convenience. The reaction mixture was stirred with a m~gnetic stirring bar for one hour at ambient temperature. Most of the solvent then was removed in a rotary evaporator and the residue was eluted from a silica gel column as already described.
The ~-cyclodextrin-transorber Colorant A inclusion complex moved down the column first, cleanly separating from both free Colorant A
and ~-cyclodextrin-transorber. The eluant cont~ining the complex was collected and the solvent removed in a rotary evaporator. The residue was subjected to a reduced pressure of 0.01 Torr to remove ~ 30 residual solvent to yield a blue-green powder.
- E. Mutation of Colored Composition The ~-cyclodextrin-transorber Colorant A inclusion complex was exposed to ultraviolet radiation from two different lamps, Lamps A and B. Lamp A was a 222-nanometer excimer lamp assembly organized in banks of four cylindrical lamps having a CA 022194~0 1997-11-17 WO 96/39646 PCI'/US96/08887 length of about 30 cm. The lamps were cooled by circ~ ting water through a centrally located or inner tube of the lamp and, as a consequence, they operated at a relatively low temperature, i.e., about 50~C. The power density at the lamp's outer surface typically is in 2he range of from about 4 to about 20 joules per square meter (J/m ). However, such range in reality merely reflects the capabilities of current excimer lamp power supplies; in the future, higher power ~len~itie~ may be practical. The distance from the lamp to the sample being irr~ ted was 4.5 cm. Lamp B was a 500-watt Hanovia medium pressure mercury lamp (Hanovia Lamp Co., Newark, New Jersey). The distance from Lalnp B to the sample being irradiated was about 15 cm.
A few drops of an N,N--limP*hylformamide solution of the ~-cyclodextrin-transorber Colorant A inclusion complex were placed on a TLC plate and in a small polyethylene weighing pan. Both s~mples were exposed to Lamp A and were decolorized (mllt~te~ to a colorless state) in 15-20 seconds. Similar results were obtained with Lamp B in 30 seconds.
A first control sample consisting of a solution of Colorant A
and ~-cyclo-ipxtrin in N,N--limPthylform~mide was not decolorized by Lamp A. A second control sample consisting of Colorant A and l-hydroxycyclohexyl phenyl ketone in N,N-dimethylformamide was decolorized by Lamp A within 60 seconds. On standing, however, the color began to re~ear within an hour.
2s To evaluate the effect of solvent on decolorization, 50 mg of the ~-cyclodextrin-transorber Colorant A inclusion complex was dissolved in 1 ml of solvent. The resulting solution or ~ ~e was placed on a glass microscope slide and exposed to Lamp A for 1 minute. The rate of decolorization, i.e., the time to render the sample colorless, was directly proportional to the solubility of the complex in the solvent, as sllmm~ri7ed below.
CA 022194~0 1997-11-17 Table 1 Solvent Solubility Decolorization Time N,N-Dimethylform~mide Poor 1 ~ e Dimethylsulfoxide Soluble <10 seconds Acetone Soluble <10 seconds Hexane Insoluble --Ethyl Acetate Poor 1 ~ llule Finally, 10 mg of the ~-cyclodextrin-transorber Colorant A
inclusion complex were placed on a glass microscope slide and crushed with a pestle. The resulting powder was exposed to Lamp A
for 10 seconds. The powder turned colorless. Similar results were obtained with Lamp B, but at a slower rate.
Example 7 Because of the possibility in the preparation of the colored composition described in the following examples for the acylated transorber acid chloride to at least partially occupy the cavity of the cyclodextrin, to the partial or complete exclusion of colorant, a modified preparative procedure was carried out. Thus, this example describes the preparation of a ~-cyclodextrin molecular includant having (1) a colorant at least partially included within the cavity of the cyclodextrin and associated therewith by means of hydrogen bonds and/or van der Waals forces, and (2) an ultraviolet radiation transorber covalently bonded to the cyclodextrin subst~nti~lly outside of the cavity of the cyclodextrin.
A . Association of Colorant with a Cyclodextrin To a solution of 10.0 g (9.8 mmole) of ~-cyclodextrin in 150 ml of N,N--lim~thylformamide was added 3.24 g (9.6 mmoles) of Colorant A. The resulting solution was stirred at ambient temperature for one hour. The reaction solution was concentrated under reduced pressure in a rotary evaporator to a volume about one-tenth of the original volume. The residue was passed over a CA 022194~0 1997-11-17 WO 96/39646 PCT/US~6/08887 silica gel column as described in Part C of Fx~mple 6. The solvent in the eluant was removed under reduced pressure in a rotary evaporator to give 12.4 g of a blue-green powder, ~-cyclodextrin Colorant A inclusion complex.
B. Covalent Bonding of Acylated Transorber to Cyclodextrin Colorant Inclusion Complex - Preparation of Colored Composition A 250-ml, three-necked, round-bottomed reaction flask containing a m~netic stirring bar and fitted with a thermometer, condenser, and pressure-eqll~li7in~ addition funnel equipped with a nitrogen inlet tube was charged with 10 g (9.6 mmole) of ~-cyclodextrin Colorant A inclusion complex, 31.6 g (98 mmoles) of l-hydroxycyclohexyl 4-(2-chloroformylethyl)carbonylphenyl ketone prepared as described in Part B of F.x~mple 6, and 150 ml of N,N-dimethylform~mide while being continuously flushed with nitrogen. The reaction mixture was he~tefl to 50~C and 0.5 ml of triethyl~mine added. The reaction mixtllre was m~int~in~-l at 50~C
for an hour and allowed to cool to ambient temperature. The reaction mixture then was worked up as described in Part A, above, to give 14.2 g of 13-cyclodextrin-transorber Colorant A inclusion complex, a blue-green powder.
C. Mutation of Colored Composition The procedures described in Part E of Example 6 were repeated with the ~-cyclo-lextrin-transorber Colorant A inclusion complex prepared in Part B, above, with essçnti~lly the same results.
li x~mple 8 This example describes a method of preparing an ultraviolet radiation transorber, 2-[p-(2-methyllactoyl)phenoxy]ethyl 1,3-dioxo-2-isoindolin~f etate, design~t~l phthaloylglycine-2959.
The following was admixed in a 250 ml, three-necked, round bottomed flask fitted with a Dean & Stark adapter with condenser and two glass stoppers: 20.5g (0.1 mole) of the wavelength selective sensitizer, phthaloylglycine (Aldrich Chemical Co., Milwaukee, WO 96~9646 PCT~US96/08887 Wisconsin); 24.6 g (0.lmole) of the photoreactor, DARCUR 2959 (Ciba-Geigy, Hawthorne, New York); 100 ml of ben~ene (Aldrich Chemical Co., Milw~llk~e7 Wisconsin); and 0.4 g p-toluenesulfonic acid (Aldrich Chemical Co., Milw~llk~e, Wisconsin). The rnixture S was heated at reflux for 3 hours after which time 1.8 ml of water was collected. The solvent was removed under reduced pressure to give 43.1 g of white powder. The powder was recryst~lli7e~1 from 30% ethyl ~cet~te in hexane (Fisher) to yield 40.2 g (93%) of a white crystalline powder having a mP.l~ing point of 153-4~C. The reaction is sllmm~ri7çd as follows:
~N{~H2co2H ~ HO--(CH2)2--~~ /CH3 p-toluene CH3 O sulfonic acid Benzene ~N--CH2C--O(cHJ2o~c\cc~H3H
The resulting product, designated phthaloylglycine-2959, had the following physical parameters:
IR [NUJOL MULL] vm~ 3440, 1760, 1740, 1680, 1600 cm-l lH NMR [CDC13] appm 1.64[s], 4.25[m], 4.49[m], 6.92[m3, 7.25[m], 7.86[m], 7.98[m], 8.06[m] ppm ~ 20 Example 9 ~ This example describes a method of dehydrating the phthaloylglycine-2959 produced in Example 8.
The following was admixed in a 250 ml round bottomed flask 2s fitted with a Dean & Stark adapter with condenser: 21.6 g (0.05 mole) phthaloylglycine-2959; 100 ml of ~nhydrous ben7P-ne (Aldrich Chemical Co., Milwaukee, Wisconsin); and 0.1 g p-toluenesulfonic acid (Aldrich Chemical Co., Milwaukee, Wisconsin). The mi~
was refluxed for 3 hours. After 0.7 ml of water had been collected in the trap, the solution was then removed under v~c~mm to yield 20.1 g (97%) of a white solid. However, analysis of the white solid showed that this reaction yielded only 15 to 20% of the desired dehydration product. The reaction is sl-mm~ri7e-1 as follows:
o XN ~H2C ~(CH2)20 ~e ~ C OH
p- toluerle sulfonic acid Benzene o G~N~H2C ~(CH2)2O~O CH;
The resulting reaction product had the following physical parameters:
IR (NUJOL) vma" 1617cm-1 (C=C-C=O) 1~
Example 10 This example describes the Nohr-MacDonald elimin~tion reaction used to dehydrate the phthaloylglycine-2959 produced in Example 8.
Into a 500 ml round bottomed flask were placed a stirring m~gnet, 20.0g (0.048 mole) of the phthaloylglycine-2959, and 6.6 g (0.048 mole) of anhydrous zinc chloride (Aldrich Chemical Co., Milwaukee, Wisconsin). 250 ml of anhydrous p-xylene (Aldrich Chemical Co., Milwaukee, Wisconsin) was added and the mixture refluxed under argon atmosphere for two hours. The reaction mixture was then cooled, resulting in a white precipitate which was collected. The white powder was then recryst~lli7e~1 from 20~o ethyl acetate in hexane to yield 18.1 g (95%) of a white powder. The reaction is ~ l ;7e-l as follows:
¢~N--CH2C--O(CH2)2~~ /CH3 H20 ZnCI2 ~
~,, p-Xylene ¢~N~H2C--O(CH2)2~~ ,~CH2 The resulting reaction product had the following physical lo parameters:
Melting Point: 138~C to 140~C.
Mass spectrum: m/e: 393 M +, 352, 326, 232, 160.
IR (KB) vm"" 1758, 1708, 1677, 1600 cm-l lH NMR [DMSO] ~ppm 1.8(s), 2.6(s), 2.8 (d), 3.8 (d), 4.6 (m), 4.8 (m), 7.3(m), 7.4 (m), 8.3 (m), and 8.6 (d) 13C NMR [DMSO] appm 65.9 (CH2=) Example 11 This example describes a method of producing a 13--cyclodextrin having dehydrated phthaloylglycine-2959 groups from Example 9 or 10 covalently bonded thereto.
The following was admixed in a 100 ml round-bottomed flask:
5.0 g (4 mmole) ,3--cyclodextrin (American Maize Product Company, Hammond, Indiana) (designated 13--CD in the following reaction); 8.3 g (20 mmole) dehydrated phthaloylglycine-2959; 50 ml of anhydrous DMF; 20 ml of benzene; and 0.01 g p--tolulenesulfonyl chloride (Aldrich Chemical Co., Milwaukee, Wisconsin). The mixture was chillP~l in a salt/ice bath and stirred for 24 hours. The reaction mixture was poured into 150 ml of weak sodium bicarbonate solution and extracted three times with 50 ml S ethyl ether. The aqueous layer was then filtered to yield a white solid comprising the ,3--cyclodextrin with phthaloylglycine-2959 group ~tt~he~l A yield of 9.4 g was obt~inlo~ Reverse phase TLC
plate using a 50:50 DMF:acetonitrile mixture showed a new product peak compared to the starting m~teri~
cyclodextrin H2C ~xCH2)20~ ~ <!H + _,~
HO--CH2'CH2/
.. ,i3 cyclodextrin ~c ~J
fl R ~H2 o--CH2~H2~
b~,~ ffH2C~)(CH2)20 ~ -~H~3H3 The ~-cyclodextrin molecule has several primary alcohols and secondary alcohols with which the phthaloylglycine-2959 can react.
1~ The above representative reaction only shows a single phthaloylglycine-2959 molecule for illustrative purposes.
Example 12 This example describes a method of assoc i~ting a colorant and an ultraviolet radiation transorber with a molecular includant. More particularly, this example describes a method of associating the colorant crystal violet with the molecular includant ,B--cyclodextrin covalently bonded to the ultraviolet radiation transorber dehydrated phthaloylglycine-2959 of Example 11.
CA 022194~0 1997-11-17 WO 96/39646 PCT/US96~1~5~g37 The following was placed in a 100 ml beaker: 4.0 g ,13--cyclodextrin having a dehydrated phthaloylglycine-2959 group; and 50 ml of water. The water was heated to 70~C at which point the solution becam~ clear. Next, 0.9 g (2.4 rnmole) crystal violet (Aldrich C'hPmical Company, Milwaukee, Wisconsin) was added to the solution, and the solution was stirred for 20 minntes. Next, the solution was then filtered. The filtrand was washed with the filtrate and then dried in a vacuum oven at 84~C. A violet-blue powder was obtained having 4.1 g (92%) yield. The resulting reaction product had the following physical parameters:
U.V. Spectrum DMF vm~ 610 nm (cf cv vm,~" 604 nm) ~y~mple 13 This example describes a method of producing the ultraviolet radiation transorber 4(4-hydroxyphenyl) butan-2-one-2959 (chloro substituted).
The following was admixed in a 250 ml round-bottomed flask fitted with a condenser and m~netic stir bar: 17.6 g (O.lmole) of the wavelength selective sen~iti7er~ 4(4-hydroxyphenyl) butan-2-one (Aldrich Chemical Company, Milwaukee, Wisconsin); 26.4 g (0.1 mole) of the photoreactor, chloro substituted DARCUR 2959 (Ciba-Geigy Corporation, Hawthorne, New York); 1.0 ml of pyridine (Aldrich Chemical Company, Milwaukee, Wisconsin); and 100 ml of anhydrous tetrahyd~orul~n (Aldrich Chemical Company, Milwaukee, Wisconsin). The mixture was refluxed for 3 hours and the solvent partially removed under reduced pressure (60% taken off). The reaction mixture was then poured into ice water and extracted with two 50 ml aliquots of diethyl ether. After drying over anhydrous magnesium sulfate and removal of solvent, 39.1 g of white solvent ~ 30 remained. Recryst~11i7~tion of the powder from 30% ethyl acetate in hexane gave 36.7 g (91%) of a white crystalline powder, having a melting point of 142-3~C. The reaction is sllmm~rized in the following reaction:
, WO 96/39646 PCI~/US96/~3~3~37 1~l ~OH + Cl(CH )~--~~cR ,CH3 CH3 ~--CH2CH2 ~~--(CH2)2_o~! CH3 The resulting reaction product had the following physical parameters:
IR [NUJOL MULL ] vm"c 3460, 1760, 1700, 1620, 1600 cm-l lH [CDCl3] appm 1.62[s],4.2[m], 4.5[m], 6.9tm] ppm The ultraviolet radiation transorber produced in this example, 4(~hydroxyphenyl) butan-2-one-2959 (chloro substituted), may be associated with ,B--cyclodextrin and a leuco dye such as the leuco form of crystal violet, using the methods described above wherein 4(4-hydroxyphenyl) butan-2-one-2959 (chloro substituted) would be substituted for the dehydrated phthaloylglycine-2959.
Example 14 Preparation of epoxide intermediate of dehydrated phthaloylglycine-The epoxide interm~ tP of dehydrated phthaloylglycine 2959 was ~ ared according to the following reaction:
CA 022l9450 l997-ll-l7 ~N--CH2C--o(cH2)2o~3lo--c,'cH;
H202/NaOH
~N--CH2 11--o(CH2)20 ~3C~o, ,CH;
In a 250 ml, three-necked, round bottomed flask fitted with an addition funnel, thermometer and magnetic stirrer was placed 30.0g (0.076 mol) of the dehydrated phthaloylglycine-2959, 70 ml methanol and 20.1 ml hydrogen peroxide (30% solution). The reac~ion rnixture was stirred and cooled in a water/ice bath to maintain a temperature in the range 15~-20~ C. 5.8 ml of a 6 N
NaOH solution was placed in the addition funnel and the solution was slowly added to m~int~in the reaction mixture tempei~LL~Ile of 15~-20~ C. This step took about 4 minlltes. The mixture was then stirred for 3 hours at about 20~-25~ C. The reaction mixtllre was then poured into 90 ml of water and extracted with two 70 ml portions of ethyl ether. The organic layers were combined and washed with 100 1~ ml of water, dried with anhydrous MgSO4 filtered, and the ether removed on a rotary evaporator to yield a white solid (yield 20.3g, 65%). The IR showed the stretching of the C-O-C group and the m~te.ri~l was used without further purification.
WO 96/:S9646 PCT/US96/08887 Example 15 Attachment of epoxide intermeL~ te to thiol cyclodextrin The ~tt~chm~nt of the epoxide intermP~ te of dehydrated phthaloylglycine 2959 was done according to the following reaction:
~N - cH2~--O(CH2)2~~H2 ~ - ,~
~ (HS--CH2CH
DMF
r 0~C Beta-CD
O o ocH3 [~N- CH2C--O(CH2)20~-CI H--CH2--(S--CH2CH2~
In a 250 ml 3-necked round bottomed flask fitted with a stopper and two glass stoppers, all being wired with copper wire and attached to the flask with rubber bands, was placed 30.0 g (0.016 mol) thiol cyclodextrin and 100 ml of ~nhydrous ~1imPIl-ylro~ mide (DMF) (Aldrich Chemical Co., Milwaukee, Wisconsin). The reaction mixture was cooled in a ice bath and 0.5 ml diisopropyl ethyl amine was added. Hydrogen sulfide was bubbled into the flask and a positive pressure m~int~in~.d for 3 hours. During the last hour, the reaction mixture was allowed to wa~n to room temperature.
The reaction mixture was flushed with argon for 15 minutes and then poured into 70 ml of water to which was then added 100 ml acetone. A white precipitate occurred and was filtered to yield 20.2 g (84.1%) of a white powder which was used without further purification.
In a 250 ml round bottomed flask fitted with a m~nP~ic stirrer and placed in an ice bath was placed 12.7 (0.031 mol), 80 ml of anhydrous DMF (Aldrich Chemical Co., Milwaukee, Wisconsin) and 15.0 g (0.010 mol) thiol CD. After the reaction l~ Lure was cooled, CA 022194~0 1997-11-17 0.5 ml of diisopropyl ethyl amine was added and the reaction mixtllre stirred for 1 hour at 0~C to 5~C followed by 2 hours at room temperature. The reaction mixture was then poured into 200 ml of ice water and a white precipitate formed immediately. This was filtered and washed with acetone. The damp white powder was dried in a convection oven at 80~C for 3 hours to yield a white powder. The yield was 24.5 g (88%).
Example 16 Insertion of Victoria Pure Blue in the cyclodextrin cavity In a 250 ml Erlenmeyer flask was placed a m~gn~tic stirrer, 40.0 g (0.014 mol) of the compound produced in Example 15 and 100 ml water. The flask was heated on a hot plate to 80~C. When the white cloudy mixture became clear, 7.43 g (0.016 mol) of lS Victoria Pure Blue BO powder was then added to the hot solution and stirred for 10 minutes then allowed to cool to 50~~. The contents were then filtered and washed with 20 ml of cold water.
The precipitate was then dried in a convention oven at 80~C
for 2 hours to yield a blue powder 27.9 g (58.1%).
Example 17 The preparation of a tosylated cyclodextrin with the dehydroxy phthaloylglycine 2959 attached thereto is performed by the following reactions:
2~
CA 022194~0 1997-11-17 WO 96/39646 PCI~/US96/08887 44 ' ~N--CH2C--O(CH2)2~~ ~CH2 ~,, DMF
¢~N--CH2C--O(CH2)2~~ ~CH2--S H
To a 500 ml 3-necked round bottomed flask fitted with a bubble tube, condenser and addition funnel, was placed 10 g (0.025 mole) of the dehydrated phthaloylglycine 2959 in 150 ml of anhydrous N,N-diethylformamide (Aldrich Chemical Co., Milwaukee, Wisconsin) cooled to 0~C in an ice bath and stirred with a m~gnetic stirrer. The synthesi~ was repeated except that the flask was allowed to warm up to 60~C using a warm water bath and the lo H2S pumped into the reaction flask till the stoppers started to move (trying to release the pressure). The flask was then stirred under these conditions for 4 hours. The saturated solution was kept at a positive pressure of H2S. The stoppers were held down by wiring and rubber bands. The reaction mixture was then allowed to warm-up overnight. The solution was then flushed with argon for 30 minutes and the reaction mixture poured onto 50 g of crushed ice and extracted three times (3 x 80 ml) with diethyl ether (Aldrich Chemical Co., Milwaukee, Wisconsin).
The organic layers were condensed and washed with water and dried with MgSO4. Removal of the solvent on a rotary evaporator gave 5.2 g of a crude product. The product was purified on a silica column using 20% ethyl acetate in hexane as eluant. 4.5 g of a white solid was obt~inP~1 A tosylated cyclodextrin was prepared according to the following reaction:
~c 7 CH3~CI
Pyridine ~, ,,~ CH2 [OTs~c To a 100 ml round bottomed flask was placed 6.0 g S ~-cyclodextrin (American Maize Product Company), lO.Og (0.05 mole) p-toluenesulfonyl chloride (Aldrich Chernical Co., Milwaukee, Wisconsin), 50 ml of pH 10 buffer solution (Fisher). The resultant trix~lre was stirred at re~ te~ u~ r 8 hol~rs after w~ch i;~
was poured on ice (approximately 100 g) and extracted with diethyl ether. The aqueous layer was then poured into 50 ml of acetone (Fisher) and the resultant, cloudy mixture filtered. The resultant white powder was then run through a sephadex colurnn (Aldrich Chemical Co., Milw~lk~e, Wisconsin) using n-butanol, ethanol, and water (5:4:3 by volume) as eluant to yield a white powder. The yield 1~ was 10.9%.
The degree of substitution of the white powder (tosyl-cyclodextrin) was determined by 13C NMR spectroscopy (DMF-d6) by comparing the ratio of hydroxysubstituted carbons versus tosylated carbons, both at the 6 position. When the 6-position carbon bears a hydroxy group, the NMR peaks for each of the six carbon atoms are given in Table 5.
WO 96/39646 PCT/US~)G1~3.5 Table ~
Carbon Atom NMR Peak (ppm) 101.8 2 72.9 3 72.3 4 81.4 71.9 6 59.8 The presence of the tosyl group shifts the NMR peaks of the S-S position and 6-position carbon atoms to 68.8 and 69.5 ppm, respectively.
The degree of substitution was calculated by integrating the NMR peak for the 6-position tosylated carbon, integrating the NMR
peak for the 6-position hydroxy-substituted carbon, and dividing the former by the latter. The integrations yielded 23.6 and 4.1, respectively, and a degree of substitution of S.9. Thus, the average degree of substitution in this example is about 6.
The tosylated cyclodextrin with the dehydroxy phthaloylglycine 2959 attached was prepared according to the following reaction:
~N--CH2C--O(CH~)*~co CH~
[~'--CH2c--O(CH2)2o~ CH3 To a 250 ml round bottomed flask was added 10.0 g (4-8 mole) of tosylated substituted cyclo~1extTin 20.7g (48 mmol) of ~iol CA 022194~0 1997-11-17 (mercapto dehydrated phthaloylglycine 2959) in 100 ml of DMF.
The reaction mixture was cooled to 0~ C in an ice bath and stirred using a m~gnetic stirrer. To the solution was slowly dropped in 10 ml of ethyl diisopropylamine (Aldrich Chemical Co., Milwaukee, s Wisconsin) in 20 ml of DMF. The reaction was kept at 0~ C for 8 hours with stirring. The reaction ~ ire was extracted with diethyl ether. The aqueous layer was then treated with S00 ml of acetone and the precipitate filtered and washed with acetone. The product was then run on a sephadex column using n-butanol, ethanol, and water (5:4:3 by volume) to yield a white powder. The yield was 16.7 g.
The degree of substitution of the functionalized molecular includant was determined as described above. In this case, the presence of the derivatized ultraviolet radiation transorber shifts the lS NMR peak of the 6-position carbon atom to 63.1. The degree of substitution was calculated by integrating the NMR peak for the 6-position substituted carbon, integrating the NMR peak for the 6-position hydroxy-substituted carbon, and dividing the forrner by the latter. The integrations yielded 67.4 and 11.7, respectively, and a degree of substitution of 5.7. Thus, the average degree of substitution in this example is about 6. The reaction above shows the degree of substitution to be "n". Although n represents the value of substitution on a single cyclodextrin, and therefore, can be from 0 to 24, it is to be understood that the average degree of substitution is about 6.
Example 18 The procedure of Example 17 was repeated, except that the amounts of ~3-cyclodextrin and p-toluenesulfonic acid (Aldrich) were - 30 6.0 g and S.0 g, respectively. In this case, the degree of substitution of the cyclodextrin was found to be about 3.
Example 19 The procedure of Example 17 was repeated, except that the 3s derivatized molecular includant of Example 18 was employed in CA 022194~0 1997-11-17 48 ' place of that from Example 17. The average degree of substitution of the function~ e~ molecular includant was found to be about 3.
F,Y~nP1e 20 This example describes the preparation of a colored composition which includes a mutable colorant and the function~li7~-1 molecular includant from Example 17.
In a 250-ml Erlenmeyer flask cont~inin~ a m~gnetic stirring bar was placed 20.0 g (5.4 mmoles) of the functionalized molecular includant obtained in Example 17 and 100 g of water. The water was heated to 80~C, at which temperature a clear solution was obt~ine-l To the solution was added slowly, with stirring, 3.1 g (6.0 mmoles) of Victoria Pure Blue BO (Aldrich). A precipitate formed which was removed from the hot solution by filtration. The precipitate was washed with 50 ml of water and dried to give 19.1 g (84 percent) of a blue powder, a colored composition consisting of a mutable colorant, Victoria Pure Blue B0, and a molec~ r includant having covalently coupled to it an average of about six ultraviolet radiation transorber molecules per molecular includant molecule.
Example 21 The procedure of Example 20 was repeated, except that the function~li7l--l molecular includant from Example 19 was employed in place of that from Example 17.
Example 22 This example describes mllt~tion or decolorization rates for the compositions of Examples 12 (wherein the ,B--cyclodextrin has dehydrated phthaloyl glycine-2959 from Example 9 covalently bonded thereto), 20 and 21.
In each case, approximately l0 mg of the composition was placed on a steel plate (Q-Panel Company, Cleveland, Ohio). Three drops (about 0.3 ml) of acetonitrile (Burdick & Jackson, Muskegon, Michigan) was placed on top of the composition and the two materials were quickly mixed with a spatula and spread out on the CA 022194~0 1997-11-17 plate as a thin film. Within 5-10 seconds of the addition of the acetonitrile, each plate was exposed to the radiation from a 222-nanometer excimer lamp assembly. The assembly consisted of a bank of four cylindrical lamps having a length of about 30 cm. The lamps were cooled by circ~ tin~; water through a centrally located or inner tube of the lamp and, as a consequence, they operated at a relatively low tempelalule, i.e., about 50~C. The power density at the lamp's outer surface typically was in the range of from about 4 to about 20 joules per square meter (J/m2). However, such range in lo reality merely reflects the capabilities of current excimer lamp power supplies; in the future, higher power densities may be practical. The distance from the lamp to the sample being irr~ te-l was 4.~ cm. The time for each film to become colorless to the eye was measured. The results are sllmm~ri7ed in Table 6.
Table 6 Decolorization Times for Various Compositions Composition ~ecolorization Times (Seconds) Example 20 Example 21 3 4 Example 12 7-8 While the data in Table 6 demonstrate the clear superiority of the colored compositions of the present invention, such data were plotted as degree of substitution versus decolorization time. The plot not only demonstrates the significant improvement of the colored compositions of the present invention when compared with 2s compositions having a degree of substitution less than three, but also indicates that a degree of substitution of about 6 is about optimllm That is, little if any improvement in decolorization time would be achieved with degrees of substitution greater than about 6.
CA 022194~0 1997-11-17 WO 96/39646 PCT/US96tO8887 Example 23 This ex~mple describes the p~ tion of a complex consisting of a mutable colorant and the derivatized molecular includant of Example 17.
s The procedure of Example 20 was repeated, except that the function~li7~-1 molecular includant of Example 17 was replaced with 10 g (4.8 mmoles) of the derivatized molecular includant of F.x~mple 17 and the amount of Victoria Pure Blue BO was reduced to 2.5 g (4.8 mmoles). The yield of washed solid was 10.8 g (86 percent) of a mutable colorant associated with the ~-cyclodextrin having an average of six tosyl groups per molecule of molecular includant.
Example 24 This example describes the preparation of a colored lS composition which includes a mutable colorant and a functionalized molecular includant.
The procedure of preparing a functionalized molecular includant of Example 17 was repe~te-l, except that the tosylated ,13-cyclodextrin was replaced with 10 g (3.8 mmoles) of the complex obtained in F.x~mple 23 and the amount of the derivatized ultraviolet radiation transorber prepared in Example 17 was 11.6 g (27 mmoles). Ihe amount of colored composition obtained was 11.2 g (56 percent). The average degree of substitution was determined as described above, and was found to be 5.9, or about 6.
Example 25 This example describes a method of preparing the following pre-dye of the present invention, wherein X represents a photoinitiator, or wherein X represents a wavelength-specific sensitizer:
N(CH3)2 CH~ 0~30CH2CH20--X
N (CH3)2 The procedure of Examples 1 and 2 is repeated except that the hydroxy ethoxy-dimethyl amino benzophenone of Example 1 is s replaced with X-oxyethoxy-dimethyl arnino benzophenone. The reactions are sllmm~n7~d as follows:
WO 96/39646 PCI~/US96/08887 (CH3)2N ~oCH2CH20X
~C=O + O=C
(CH3)2N N(CH3)2 Mg/HgCI2/RIo.n7~n~.
(cH3)2N N(CH3)2 (CH3)2N ~--C ~ OCH2CH20X
N(CH3)2 (CH3)2N~ ~OCH2CH20X
¢~
N(CH3)2 Example 26 This example describes the preparation of the following pre-S dye.
N(CH3)2 N~C-C:~O(CH ) 0~ ~ ~~~ CH3 CH3 ¢~ 2 2 ~N--CH2Co(CH2)20~3C-C--OH
N(CH3)2 The above pre-dye is prepared as s~lmm~ri7ed below in steps A, B and C.
A.
HO~ p( fi)Acetic Acid \~
I l I O + H2NCH2COH 3 l I I ,NCH2COH
Reflux B.
HO~ICH2COH + Ho(CH2)2o~3c--C~ OH
O R~,n7P-nP.
Toll-nP.nPs~ honic Acid ~O\¢~CH2CO(CHz)20 ~C~ C\&CHO3H
The triarylmethane product prepared in Example 2 is reacted with the reaction product of step B as sllmm~ri7e~1 in reaction step C
below.
S C.
Ho~NCH2co(cH2)2o~3fi) ,CH3 N(CH3)2 (CH3)2N~c~ocH2cH2oH
N(CH3)z Williamson E~er Synthesis Nl(CH3)2 (CH3)2N ~C~3o(cH2)2~NcH2co(cH2)2(~c--C~--OH
N(CH3)2 Example 27 This example describes the preparation of the following pre-dye, wherein X represents a radiation transorber, and wherein R
represents a hydrogen, methyl, or ethyl group.
'. ~
R2N~C--C--X
The procedure of Examples 1 and 2 is repeated except that the hydroxy ethoxy-dimethyl amino benzophenone and bis dimethylaminobenzophenone of Exarnple 1 is replaced with the reactants in the reaction s~lmm~n7ed as follows:
SUBSTITUTE SHEET
R2~
~NR2 R2N~C=O + ~ = C~x Mg/HgCl2/Benzene R2N, ~R2 R~N~C--C--X
~2~Q4 R2N~ --C--X
~' Having thus described the invention, numerous changes and modifications hereof will be readily apparent to those having ordinary skill in the art.
~ a-~5~ r~
Claims (25)
1. A pre-dye composition comprising a pre-dye molecule comprising a dye covalently bound to a radiation transorber adapted so that the pre-dye molecule is colorless and will form a color when irradiated with radiation, the radiation transorber comprising a wavelength-selective sensitizer covalently bonded to a reactive species-generating photoreactor.
2. The pre-dye composition Claim 1, wherein the dye is an aminotriarylmethane or a derivative thereof.
3. The pre-dye composition of Claim 1, wherein the photoreactor is 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propan-1-one having the following formula or 1-hydroxycyclohexane phenyl ketone having the following formula
4. The pre-dye composition of Claim 1, wherein the wavelength-selective sensitizer is phthaloylglycine having the following formula or 4-(4-Hydroxy phenyl) butan-2-one having the following formula .
5. The pre-dye composition of Claim 1, wherein the radiation transorber is 2-(p-(2-methyllactoyl)phenoxy)ethyl 1,3-dioxo-2-isoindoline-acetate having the formula , phthaloylglycyl-cyclohexylphenyl ketone ester having the formula , 4-(4-oxyphenyl)-2-butanone-1-(4-(2-oxyethoxy)phenyl)-2-hydroxy-2-methyl-propan-1-one (or 2-hydroxy-2-methyl-4'-(2-(p-(3-oxobutyl)phenoxy)ethoxy)-propiophenone) having the formula , or 4-(4-oxyphenyl)-2-butanonecyclohexyl-phenyl ketone (or 4-(p-((4-benzoylcyclohexyl)oxy)phenyl)-2-butanone) having the formula
6. The pre-dye composition of Claim 1, wherein the dye is crystal violet, and the pre-dye molecule has the following formula wherein X represents a radiation transorber.
7. The pre-dye composition of Claim 6, wherein the pre-dye molecule has the formula , , , , or .
8. The pre-dye composition of Claim 1, wherein the pre-dye molecule has the formula .
or wherein X represents the radiation transorber, and wherein R
represents a hydrogen, methyl, or ethyl group.
or wherein X represents the radiation transorber, and wherein R
represents a hydrogen, methyl, or ethyl group.
9. A method of developing a color comprising:
providing a pre-dye composition comprising a pre-dye molecule comprising a dye covalently bound to a radiation transorber adapted so that the pre-dye molecule is colorless and will form a color when irradiated with radiation, the radiation transorber comprising a wavelength-selective sensitizer covalently bonded to a reactive species-generating photoreactor; and irradiating the pre-dye composition with radiation at a wavelength and dosage level sufficient to irreversibly mutate the pre-dye molecule.
providing a pre-dye composition comprising a pre-dye molecule comprising a dye covalently bound to a radiation transorber adapted so that the pre-dye molecule is colorless and will form a color when irradiated with radiation, the radiation transorber comprising a wavelength-selective sensitizer covalently bonded to a reactive species-generating photoreactor; and irradiating the pre-dye composition with radiation at a wavelength and dosage level sufficient to irreversibly mutate the pre-dye molecule.
10. The method of Claim 9, wherein the dye is an aminotriarylmethane or a derivative thereof.
11. The method of Claim 9, wherein the photoreactor is 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propan-1-one having the following formula or 1-hydroxycyclohexane phenyl ketone having the following formula .
12. The method of Claim 9, wherein the wavelength-selective sensitizer is phthaloylglycine having the following formula or 4-(4-Hydroxy phenyl) butan-2-one having the following formula .
13. The method of Claim 9, wherein the radiation transorber is 2-(p-(2-methyllactoyl)phenoxy)ethyl 1,3-dioxo-2-isoindoline-acetate having the formula , phthaloylglycyl-cyclohexylphenyl ketone ester having the formula , 4-(4-oxyphenyl)-2-butanone-1-(4-(2-oxyethoxy)phenyl)-2-hydroxy-2-methyl-propan-1-one (or 2-hydroxy-2-methyl-4'-(2-(p-(3-oxobutyl)phenoxy)ethoxy)-propiophenone) having the formula , or 4-(4-oxyphenyl)-2-butanonecyclohexyl-phenyl ketone (or 4-(p-((4-benzoylcyclohexyl)oxy)phenyl)-2-butanone) having the formula .
14. The method of Claim 9, wherein the dye is crystal violet, and the pre-dye molecule has the following formula .
wherein X represents a radiation transorber.
wherein X represents a radiation transorber.
15. The method of Claim 14, wherein the pre-dye molecule has the formula , , , , or .
16. A mutable dye composition comprising a leuco dye admixed with a radiation transorber comprising a wavelength-selective sensitizer covalently bonded to a reactive species-generating photoreactor.
17. The mutable dye composition of Claim 16, wherein the leuco dye is a leuco aminoarylmethane or a derivative thereof.
18. The mutable dye composition of Claim 16, wherein the photoreactor is 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propan-1-one having the following formula or 1-hydroxycyclohexane phenyl ketone having the following formula .
19. The mutable dye composition of Claim 16, wherein the wavelength-selective sensitizer is phthaloylglycine having the following formula or 4-(4-Hydroxy phenyl) butan-2-one having the following formula .
20. The mutable dye composition of Claim 16, wherein the radiation transorber is 2-(p-(2-methyllactoyl)phenoxy)ethyl 1,3-dioxo-2-isoindoline-acetate having the formula , phthaloylglycyl-cyclohexylphenyl ketone ester having the formula , 4-(4-oxyphenyl)-2-butanone-1-(4-(2-oxyethoxy)phenyyl)-2-hydroxy-2-methyl-propan-1-one (or 2-hydroxy-2-methyl-4'-(2-(p-(3-oxobutyl)phenoxy)ethoxy)-propiophenone) having the formula , or 4-(4-oxyphenyl)-2-butanonecyclohexyl-phenyl ketone (or 4-(p-((4-benzoylcyclohexyl)oxy)phenyl)-2-butanone) having the formula .
21. A method of developing a color comprising:
providing a composition comprising a leuco dye admixed with a radiation transorber comprising a wavelength-selective sensitizer covalently bonded to a reactive species-generating photoreactor;
and irradiating the composition with radiation at a wavelength and dosage level sufficient to irreversibly mutate the leuco dye.
providing a composition comprising a leuco dye admixed with a radiation transorber comprising a wavelength-selective sensitizer covalently bonded to a reactive species-generating photoreactor;
and irradiating the composition with radiation at a wavelength and dosage level sufficient to irreversibly mutate the leuco dye.
22. The method of Claim 21, wherein the leuco dye is a leuco aminoarylmethane or a derivative thereof.
23. The method of Claim 21, wherein the photoreactor is 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propan-1-one having the following formula or 1-hydroxycyclohexane phenyl ketone having the following formula .
24. The method of Claim 21, wherein the wavelength-selective sensitizer is phthaloylglycine having the following formula or 4-(4-Hydroxy phenyl) butan-2-one having the following formula .
25. The method of Claim 21, wherein the radiation transorber is 2-(p-(2-methyllactoyl)phenoxy)ethyl 1,3-dioxo-2-isoindoline-acetate having the formula , phthaloylglycyl-cyclohexylphenyl ketone ester having the formula , 4-(4-oxyphenyl)-2-butanone-1-(4-(2-oxyethoxy)phenyl)-2-hydroxy-2-methyl-propan-1-one (or 2-hydroxy-2-methyl-4'-(2-(p-(3-oxobutyl)phenoxy)ethoxy)-propiophenone) having the formula , or 4-(4-oxyphenyl)-2-butanonecyclohexyl-phenyl ketone (or 4-(p-((4-benzoylcyclohexyl)oxy)phenyl)-2-butanone) having the formula .
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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US08/463,187 | 1995-06-05 | ||
US08/649,754 | 1996-05-29 | ||
US08/649,754 US5786132A (en) | 1995-06-05 | 1996-05-29 | Pre-dyes, mutable dye compositions, and methods of developing a color |
Publications (1)
Publication Number | Publication Date |
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CA2219450A1 true CA2219450A1 (en) | 1996-12-12 |
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ID=27040572
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Application Number | Title | Priority Date | Filing Date |
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CA002219450A Abandoned CA2219450A1 (en) | 1995-06-05 | 1996-06-05 | Novel pre-dyes |
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US (2) | US5837429A (en) |
EP (1) | EP0830638B1 (en) |
JP (1) | JP2001515524A (en) |
AT (1) | ATE195815T1 (en) |
AU (1) | AU6378696A (en) |
BR (1) | BR9608367A (en) |
CA (1) | CA2219450A1 (en) |
DE (1) | DE69609967T2 (en) |
ES (1) | ES2148776T3 (en) |
MX (1) | MX9709250A (en) |
PL (1) | PL323727A1 (en) |
RU (1) | RU2170943C2 (en) |
SK (1) | SK160497A3 (en) |
WO (1) | WO1996039646A1 (en) |
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- 1996-06-05 EP EP96923216A patent/EP0830638B1/en not_active Expired - Lifetime
- 1996-06-05 BR BR9608367A patent/BR9608367A/en not_active Application Discontinuation
- 1996-06-05 AT AT96923216T patent/ATE195815T1/en not_active IP Right Cessation
- 1996-06-05 CA CA002219450A patent/CA2219450A1/en not_active Abandoned
- 1996-06-05 US US08/659,497 patent/US5837429A/en not_active Expired - Fee Related
- 1996-06-05 PL PL96323727A patent/PL323727A1/en unknown
- 1996-06-05 RU RU98100245/04A patent/RU2170943C2/en not_active IP Right Cessation
- 1996-06-05 WO PCT/US1996/008887 patent/WO1996039646A1/en active IP Right Grant
- 1996-06-05 SK SK1604-97A patent/SK160497A3/en unknown
- 1996-06-05 DE DE69609967T patent/DE69609967T2/en not_active Expired - Fee Related
- 1996-06-05 ES ES96923216T patent/ES2148776T3/en not_active Expired - Lifetime
- 1996-06-05 MX MX9709250A patent/MX9709250A/en not_active IP Right Cessation
- 1996-06-05 AU AU63786/96A patent/AU6378696A/en not_active Abandoned
-
1998
- 1998-11-16 US US09/192,628 patent/US6063551A/en not_active Expired - Fee Related
Also Published As
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MX9709250A (en) | 1998-03-31 |
DE69609967T2 (en) | 2001-04-12 |
AU6378696A (en) | 1996-12-24 |
PL323727A1 (en) | 1998-04-14 |
WO1996039646A1 (en) | 1996-12-12 |
SK160497A3 (en) | 1998-06-03 |
BR9608367A (en) | 1998-08-18 |
US5837429A (en) | 1998-11-17 |
ATE195815T1 (en) | 2000-09-15 |
EP0830638B1 (en) | 2000-08-23 |
US6063551A (en) | 2000-05-16 |
ES2148776T3 (en) | 2000-10-16 |
DE69609967D1 (en) | 2000-09-28 |
JP2001515524A (en) | 2001-09-18 |
RU2170943C2 (en) | 2001-07-20 |
EP0830638A1 (en) | 1998-03-25 |
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