| PATENT ASSIGNEE'S COUNTRY | USA |
| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | 21.03.2000 |
| PATENT TITLE |
Oxyalkylene-substituted aminophenol intermediate |
| PATENT ABSTRACT |
This invention relates to very specific oxyalkylene-substituted aminophenol compounds as intermediates for the production of poly(oxyalkylene)-substituted xanthene (or other type) colorants. Such an inventive intermediate compound is produced in a single step by reacting an oxyalkylene oxide having from 3 to 12 carbon atoms (branched or unbranched), glycidol, or a glycidyl directly with aminophenol without the use of a catalyst and at a relatively low temperature. Propylene oxide and m-aminophenol are the preferred reactants. The propylene oxide selectively reacts with the amine group on the m-aminophenol without propoxylating the phenolic hydroxyl group. Such a specific method thus does not require extra time- and cost-consuming steps of protecting the phenolic hydroxyl group from attack. After production, this intermediate may be reacted with suitable compounds to ultimately form any number of different colorants, including xanthenes, oxazines, coumarins, and the like. The resultant oxypropylene groups may subsequently be reacted with electrophile compounds to produce any number of different colorants. Resultant colorants produced through the reaction of the inventive intermediate are also contemplated within this invention. |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | March 5, 1999 |
| PATENT CLAIMS |
What we claim is: 1. An aminophenol intermediate comprising at most a total of three moles of a constituent selected from the group of oxyalkylenes having from 3 to 12 carbon atoms, alkoxyalkylesters having from 3 to 12 carbon atoms, glycidol, and a glycidyl group wherein said constituent is solely bonded to the amine. 2. The intermediate of claim 1 further defined by the Formula (I) ##STR9## wherein x and y are the same or different and are 0, 1, or 2, and wherein x+y is greater than 0 and less than 4; wherein R is selected from the group consisting of hydrogen, halo, formyl, C.sub.1 -C.sub.20 alkoxy, and C.sub.1 -C.sub.20 alkyl; wherein R' is selected from the group consisting of C.sub.1 -C.sub.10 alkoxy, C.sub.1 -C.sub.10 polyoxyalkoxy, C.sub.1 -C.sub.10 alkylester, and C.sub.1 -C.sub.10 alkyl; and wherein R" is H or CH.sub.2 R'. 3. The compound of claim 1 wherein x and y are both 1; R is selected from the group consisting of hydrogen, C.sub.1 -C.sub.4 alkoxy, and C.sub.1 -C.sub.4 alkyl; R' is selected from methyl and ethyl; and R" is H. 4. The compound of claim 3 wherein R is hydrogen and R' is methyl. 5. A method of making an aminophenol intermediate comprising the steps of providing an aminophenol compound and directly reacting to said aminophenol at most three moles of a constituent selected from the group consisting of alkylene oxide containing having from 3 to 12 carbon atoms, glycidol, and a glycidyl group. 6. The method of claim 5 wherein said aminophenol inter-mediate is further defined by the Formula (I) ##STR10## wherein x and y are the same or different and are 0, 1, or 2, and wherein x+y is greater than 0 and less than 4; wherein R is selected from the group consisting of hydrogen, halo, formyl, C.sub.1 -C.sub.20 alkoxy, and C.sub.1 -C.sub.20 alkyl; wherein R' is selected from the group consisting of C.sub.1 -C.sub.10 alkoxy, C.sub.1 -C.sub.10 polyoxyalkoxy, C.sub.1 -C.sub.10 alkylester, and C.sub.1 -C.sub.10 alkyl; and wherein R" is H or CH.sub.2 R'; and wherein said aminophenol is further defined by the Formula (II) ##STR11## wherein R is selected from the group consisting of hydrogen, halo, C.sub.1 -C.sub.20 alkoxy, and C.sub.1 -C.sub.20 alkyl. 7. The method of claim 5 wherein the direct reaction is performed at a reaction temperature of from about 120 to about 250.degree. F. 8. The method of claim 6 wherein x and y are both 1; wherein R is selected from the group consisting of hydrogen, C.sub.1 -C.sub.4 alkoxy, and C.sub.1 -C.sub.4 alkyl; wherein R' is selected from the group consisting methyl and ethyl; and wherein R" is H. 9. The method of claim 8 wherein R is hydrogen and wherein R' is methyl. 10. The method of claim 9 wherein the reaction temperature is about 150 to about 200.degree. F. 11. A xanthene colorant produced through the reaction of the intermediate of claim 2 and at least one other reactant compound selected from the group consisting of a phthalic anhydride and a benzaldehyde. 12. The xanthene colorant of claim 11 wherein said at least one other reactant compound is phthalic anhydride. 13. An oxazine colorant produced through the reaction of the intermediate of claim 2 and a nitrosated derivative of said intermediate. 14. A coumarin colorant produced through the reaction of the intermediate of claim 2 and ethylcyanoacetate. 15. A coumarin colorant produced through the reaction of the intermediate of claim 2 and both an ethylcyanoacetate and a phenylenediamine. |
| PATENT DESCRIPTION |
FIELD OF THE INVENTION This invention relates to very specific oxyalkylene-substituted aminophenol compounds as intermediates for the production of poly(oxyalkylene)-substituted xanthene (or other type) colorants. Such an inventive intermediate compound is produced in a single step by reacting an oxyalkylene oxide or oxyalkylester having from 3 to 12 carbon atoms (branched or unbranched), glycidol, or a glycidyl directly with aminophenol without the use of a catalyst and at a relatively low temperature. Propylene oxide and m-aminophenol are the preferred reactants. The propylene oxide selectively reacts with the amine group on the m-aminophenol without propoxylating the phenolic hydroxyl group. Such a specific method thus does not require extra time- and cost-consuming steps of protecting the phenolic hydroxyl group from attack. After production, this intermediate may be reacted with suitable compounds to ultimately form any number of different colorants, including xanthenes, oxazines, coumarins, and the like. The resultant oxypropylene groups may subsequently be reacted with electrophile compounds to produce any number of different colorants. Resultant colorants produced through the reaction of the inventive intermediate are also contemplated within this invention. DISCUSSION OF THE PRIOR ART All U.S. and foreign patents cited within this specification are hereby incorporated by reference. Xanthene colorants provide red, bluish red, and magenta tints within the colorant industry. However, the versatility of such colorants within and on different substrates had proven difficult to accomplish in the past. It was believed that the ability to potentially increase the number of available substrates for which such colorants could be used was possible upon the addition of oxyalkylene groups to the colorant itself. Such a reaction is not possible with the already formed xanthene system. However, it was theorized that the formation of an oxyalkylenated aminophenol intermediate could provide the desired effect upon production of the xanthene from the intermediate. Such an intermediate was first produced in U.S. Pat. No. 5,250,708 to Barry, Jr. and provided the ability of producing such desirable xanthene derivative colorants. Thus, poly(oxyalkylenated) xanthene colorants have only recently been made available to the colorant market. However, even with the intermediate provided by the '708 patent, the limiting factor in producing such colorants has still proven to be the cost- and time-effective formation of a poly(oxyalkylenated) aminophenol intermediate which would subsequently react with phthalic anhydride to form the desired poly(oxyalkylenated) xanthene derivative compound. Patentee formed the intermediate, which required at least 6 moles of alkylene oxide to be reacted to form the desired oxyalkylenated intermediate, through a five-step process which included the protection of the phenolic hydroxyl group from attack by the alkylene oxide compounds. This entire cumulative reaction has thus proven cumbersome, time-consuming, and costly. There thus exists a need to improve upon this procedure and potentially to produce a novel intermediate which ultimately provides the same ability of forming highly desirable oxyalkylenated xanthene colorants but does not require a multi-step process in forming the intermediate alone. The prior art has not accorded such an improvement within this specific area of colorant chemistry. DESCRIPTION OF THE INVENTION It is thus an object of the invention to provide a specific oxyalkylenated aminophenol intermediate for the production of an oxyalkylenated xanthene colorant. It is another object of this invention to provide a method of forming a specific propoxylated aminophenol intermediate which is a one-step process. A further object of the invention is to provide a specific propoxylated aminophenol intermediate which will not alternatively form a xanthene dyestuff upon reaction with phthalic anhydride and thus provides excellent yield of the desired colorant alone. Yet another object of this invention is to provide a relatively inexpensive method for producing such beneficial oxyalkylenated xanthene (or other type) colorants, the physical and chemical properties of which can be easily modified through subsequent reaction of the free hydroxyl groups with electrophiles such as anhydrides, isocyanates, esters, benzochlorides, and the like. Accordingly, the present invention encompasses an aminophenol intermediate comprising at most a total of three moles of a constituent selected from the group of oxyalkylene groups having from 3 to 12 carbon atoms, alkoxy alkylester groups having from 3 to 12 carbon atoms, glycidol, and a glycidyl group wherein said constituent is solely bonded to the amine. The method of producing such a specific oxyalkylenated aminophenol intermediate is contemplated within this invention as well. The amine constituent may reside in any position relative to the phenol on the benzene ring (i.e., p-aminophenol, o-aminophenol, or m-aminophenol); however, aminophenol); however, m-aminophenol is preferred. Thus, the preferred m-aminophenol intermediate is also contemplated within this invention as is the method of making such a compound, as defined by the Formula (I) ##STR1## wherein x+y is greater than 0 and less than 4; wherein R is selected from the group consisting of hydrogen, halo, formyl, C.sub.1 -C.sub.20 alkoxy, and C.sub.1 -C.sub.20 alkyl; wherein R' is selected from the group consisting of C.sub.1 -C.sub.10 alkoxy, C.sub.1 -C.sub.10 polyoxyalkoxy, C.sub.1 -C.sub.10 alkylester, and C.sub.1 -C.sub.10 alkyl; and wherein R" is H or CH.sub.2 R'; said method comprising the reaction of at most 3 moles of a compound selected from the group consisting of an alkylene oxide having from 3 to 10 carbon atoms and glycidol with a m-aminophenol compound of the Formula (II) ##STR2## wherein R is selected from the group consisting of hydrogen, halo, C.sub.1 -C.sub.20 alkoxy, and C.sub.1 -C.sub.20 alkyl, a reaction temperature of from about 120 to about 250.degree. F. The invention also covers the actual compound of Formula (I), above as well. Preferably R above (for both I and II) is hydrogen, C.sub.1-4 alkoxy, or C.sub.1-4 alkyl; most preferably R' is hydrogen. Also, preferably R" is methyl or ethyl (most preferably methyl), and R" is preferably H. It has surprisingly been found that the aforementioned method produces the desired oxyalkylenated aminophenol compound without resulting in the formation of oxyalkylene groups on the phenolic hydroxyl group. The standard reactions followed in the past to attach oxyalkylene groups to amino or hydroxyl pendant groups have included reactions with ethylene oxide without any base present. The resultant reactions thus quickly drive the addition of the oxyalkylene groups to the undesired phenolic hydroxyl sites. In the inventive method, direct reaction with less reactive longer-chain alkylene oxides is utilized to effectuate the desired reaction without simultaneously driving the attack of longer-chain oxyalkylene groups to the phenolic hydroxyl moiety. Furthermore, the relatively low reaction temperature utilized (from about 120 to about 250.degree. F.) also permits greater selectivity in the reaction of the longer-chain alkylene oxide by "slowing" the overall reaction. Comparative temperatures utilized for ethylene oxide additions are much higher (i.e., 280 to 320.degree. F.). In turn, then, the ability to perform such a procedure in a one-step process translates into lower costs for the manufacturer of the ultimately produced colorant (i.e., xanthene-derivative colorants) as well as for the end-user of products colored with such compounds. Preferably, the reaction temperature utilized to form the intermediate ranges from about 150 to about 200.degree. F. This range is optimum for the desired selectivity of the preferred propylene oxide reaction only with the amine hydrogens and not the phenolic hydroxyl group. The tower the temperature, theoretically the greater selectively, but cost-effectiveness is compromised as the reaction takes too long to accomplish. Higher temperatures (above 250.degree., preferably above 200.degree.) speed up the reaction too much so as to result in the unwanted reaction between the propylene oxide and the phenolic hydroxyl group. In order for this reaction to be successful, preferably from 2 to 3 motes of an alkylene oxide having from 3 to 10 carbon atoms (branched or unbranched and again, preferably propylene oxide) or glycidol in relation to the m-aminophenol starting material may be utilized. Greater molar amounts of the alkylene oxide will require inordinate and thus highly undesirable and costly amounts of time to produce the target oxypropylenated intermediate. Any amount below 1 mole will not provide sufficient propylene oxide to properly generate the desired oxypropylenated intermediate. This reaction appears to work with any aminophenol compound, although highly preferred is a m-aminophenol compound conforming with the Formula (II) ##STR3## wherein R is selected from the group consisting of hydrogen, halo, C.sub.1 -C.sub.20 alkoxy, and C.sub.1 -C.sub.20 alkyl. Again, in each instance, the 1 to 3 moles of, for instance, propylene oxide (per m-aminophenol compound) when directly reacted with the starting aminophenol reactant at a suitable relatively low temperature, will only attack the amino groups, thereby Producing an oxypropyl-substituted aminophenol having at most an average of 1.5 monomers (i.e., 2 monomers on one site and 1 monomer on the other) of propylene oxide added per carbon-nitrogen bond of the amino moiety. The terms "directly reacted" or "direct reaction" regarding the longer-chain alkylene oxide reaction with the starting aminophenol is intended to mean a reaction including only those materials and no catalyst or water. Certain stabilizing compounds, such as methylimidazoles, and the like, and inert solvents, such as diglymne, and the like, may be present; however, the standard base catalysts and/or water is strictly avoided in this invention method to form the desired oxypropylated aminophenol intermediate. The resultant intermediate of Formula (I) can then be reacted with at least one other reactant compound to form any number of different colorants. For instance, this intermediate may be reacted with phthalic anhydride (as discussed in U.S. Pat. No. 5,250,708, for example) to produce a xanthene-derivative compound. Alternatively, xanthene colorants may be formed through the reaction of at least 2 moles of the inventive intermediate with one note of a benzaldehyde (preferably one with carboxylic or sulfonate groups attached, such as benzaldehyde-2,4-disulfonic acid), as taught within the Barry, Jr. patent., as well as through the reaction of other compounds, such as, as merely an example, o-formyl-benzenesulfonic acid. The oxypropylene groups present on the nitrogens of the preferred xanthene derivative may then be reacted with other electrophilic and/or oxyalkylene groups in order to produce any polyoxyalkylenated xanthene colorant. This intermediate thus facilitates the production of any polyoxyalkylenated-xanthene colorant for use in any number of different media and/or on a myriad of substrates. Furthermore, the inventive intermediate will not alternatively form the correlative xanthene dyestuff during the reaction with phthalic anhydride. Such a dyestuff is highly regulated and poses potential toxicity problems and thus it is desirable to avoid production of such a compound. Furthermore, the dyestuff cannot be modified physically and/or chemically since there are no remaining reactive sites at which electrophilic groups may be attached. Because of the presence of oxypropylene groups, the phthalic anhydride only reacts with the phenolic hydroxyl group of the aminophenol, in turn forming the desired xanthene colorant and not the dyestuff. For example, U.S. Pat. No. 5,250,708 also teaches a method of producing a poly(oxyalkylene) xanthene colorant by reacting 2-(4-N,N-diethylamine-2-hydroxy benzoyl) benzoic acid with 3-methoxy-N,N-di(polyoxyalkylene oxide) aniline. The benzoic acid intermediate is produced in a reversible reaction from N,N-diethyl-m-aminophenol and phthalic anhydride. Since some residual diethyl-m-aminophenol may be present during this subsequent reaction, the intermediate may react with the N,N-diethyl-m-aminophenol to form the xanthene dyestuff. In the inventive method, such dyestuff formation is prevented since there is no use or production of N,N-diethyl-m-aminophenol. The inventive method and the inventive intermediate therefore provide clear distinct advantages over the previously disclosed xanthene compounds production methods. Additionally, the inventive intermediate can be reacted with other reactant compounds to form other types of colorants. For example, an oxazine colorant may be formed by nitrosating one mole of the inventive intermediate and subsequently reacting that reactant compound with a second mole of the inventive intermediate. As with the xanthene colorants, above, the free hydroxyl groups may then be reacted with electrophilic or oxyalkylene groups to form different oxazine derivatives. Furthermore, other colorants may also be formed, such as coumarins, through the reaction of the inventive intermediate with other reactant compounds such as, without limitation, ethylcyanoacetate and phenylenediamine. Upon production of the target coumarin, as with the aforementioned colorants, the free hydroxyl groups may then be subsequently reacted with electrophilic or oxyalkylene groups to form different coumarin derivatives. DESCRIPTION OF THE PREFERRED EMBODIMENT The preferred embodiments of this invention are provided below: Intermediate Formation The general method of making the preferred inventive intermediate is as follows: |
| PATENT EXAMPLES | This data is not available for free |
| PATENT PHOTOCOPY | Available on request |
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