Method of making sulfanatophenyl substituted porphines

Details Method of making sulfanatophenyl substituted porphines Method of making sulfanatophenyl substituted porphines

1998-12-11

2002-06-04

Shah, Mukund J. (Department: 1624)

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

Reexamination Certificate

active

06399769

ABSTRACT:

TECHNICAL FIELD
The present invention relates to an improved method for making 5,10,15,20-tetraphenyl-21H,23H-porphine-p-p
1
,p
11
,p
111
-tetrasulfonic acid, tetrasodium salt (designated p-TPPS4). The present invention is also directed to a method of making Cu-meso-tetra-(4-sulfanatophenyl)-porphine (designated p-CuTPPS4) from p-TPPS4. The improved process allows the production of p-CuTPPS4 at lower cost and higher yields compared to conventional methods of making p-CuTPPS4. The present invention further relates to a method of making 5,10,15,20-tetraphenyl-21H,23H-porphine-o,o
1
,o
11
,o
111
-tetrasulfonic acid, tetrasodium salt (designated p-TPPS4). The present invention is further directed to a method of making Cu-meso-tetra-(2-sulfanatophenyl)-porphine (designated o-CuTPPS4) from o-TPPS4 and the use of o-CuTPPS4 as a colorant stabilizer for a variety of colorants, especially magenta colorants. The o-CuTPPS4, according to the present invention, provides a more stable and more “blue” colorant stabilizer compared to known colorant stabilizers, such as Cu-meso-tetra-(p-phenylcarboxylic acid)-porphine.
BACKGROUND OF THE INVENTION
U.S. patent applications Ser. No. 08/757,222 filed Nov. 27, 1996; Ser. No. 08/788,863 filed Jan. 23, 1997; Ser. No. 08/843,410 filed Apr. 15, 1997; Ser. No. 08/903,911 filed Jul. 31, 1997; Ser. No. 60/055,785 filed Aug. 15, 1997; and Ser. No. 60/062,643 filed Oct. 22, 1997, all of which are assigned to Kimberly Clark Worldwide, Inc., disclose the use of a variety of porphines as colorant stabilizers. Porphines disclosed in the above-referenced applications include, but are not limited to, porphines having the following general structure:
wherein R is any proton-donating moiety and M is iron, cobalt or copper. Desirably, R is SO
3
H,
COOH, or R
1
COOH wherein R
1
is an alkyl group of from 1 to 6 carbons. R may also be in its corresponding
One such porphine is Cu-meso-tetra-(4-sulfanatophenyl)-porphine (designated p-CuTPPS4) having the following structure:
Conventional methods of making p-CuTPPS4 involve the following three-step process:
The yield of p-CuTPPS4 in the above process is only about 10%. In addition, the resulting product comprises a mixture of porphine molecules containing from one to four sulfonic acid groups per molecule.
An attempt to make o-CuTPPS4 is disclosed in Treibs et al.,
Leibigs Ann. Chem.,
718, 183, 1998 (hereafter, “Treibs”). Treibs tried to prepare o-TPPS4 from 2-formylbenzenesulfonic acid, pyrrole, and propionoic acid. However, Treibs could not isolate the resulting product. Treibs reported a yield by GLC analysis of less than about 10%.
Although porphines provide excellent light stability to all colorants, some porphines are relatively unstable and/or tend to “yellow” colorant compositions containing magenta dyes. A more desirable porphine molecule would be one that has less tendency to “yellow” a colorant composition, and moreover, to make the colorant composition more “blue.”
Therefore, there exists a need in the art for a convenient, low cost, high yield method of making p-TPPS4, p-CuTPPS4, and compositions containing p-CuTPPS4. There also exists a need in the art for a convenient, low cost, high yield method of making o-TPPS4, o-CuTPPS4, and compositions containing o-CuTPPS4. Further, there exists a need for improved porphines which are capable of providing superior colorant stability while being more stable and without the tendency to “yellow” colorant compositions containing magenta dyes.
SUMMARY OF THE INVENTION
The present invention addresses the needs described above by providing processes of making p-TPPS4 and o-TPPS4 at a lower cost and higher yields. The present invention also relates to processes of making Cu-meso-tetra-(4-sulfanatophenyl)-porphine (designated p-CuTPPS4) and Cu-meso-tetra-(2-sulfanatophenyl)-porphine (designated o-CuTPPS4), and the use of p-CuTPPS4 and o-CuTPPS4 as colorant stabilizers for a variety of colorants, especially magenta colorants. o-CuTPPS4 has excellent stability and provides superior stability to a variety of colorants. Moreover, o-CuTPPS4 does not “yellow” magenta dyes. Consequently, less unstable dye, such as Acid Red 52, needs to be used to make a magenta composition more “blue.” The result is a more “blue” magenta color and a higher porphine to dye ratio, which creates superior light stability.
The present invention also relates to colorant compositions having improved stability, wherein the colorant is associated with p-CuTPPS4 and/or o-CuTPPS4. These and other features and advantages of the present invention will become apparent after a review of the following detailed description of the disclosed embodiments and the appended claims.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a convenient, fast, low cost, environmental-friendly process of making p-CuTPPS4 and o-CuTPPS4. One. process of making p-CuTPPS4 proceeds by the following reaction:
The above process produces p-CuTPPS4 at yields of about 45% compared to conventional methods of producing p-CuTPPS4, which have yields of about 20%. The result is a p-CuTPPS4 having a reduction in the cost of manufacture of approximately 50%.
The reaction conditions for the above process may vary. Typically, the reaction is carried out as follows. The reactants are mixed at room temperature. The mixture is then heated, while stirring, under reflux for about one hour. A precipitate forms during the reaction. The reaction mixture is then filtered while hot to obtain the desired p-CuTPPS4. The solid is washed with hot solvent to yield a pure product.
The choice of solvent in the above process may be any aliphatic acid having from one to six carbon atoms in the carbon chain. Suitable acids include, but are not limited to, acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, formic acid, and mixtures thereof.
The present invention is also directed to a process of making Cu-meso-tetra-(2-sulfanatophenyl)-porphine (designated o-CuTPPS4). The process of making o-CuTPPS4 proceeds by the following reaction:
The above process produces o-CuTPPS4 at yields of about 55%. The resulting o-CuTPPS4 ha s excellent stability and provides superior stability to a variety of colorants. Moreover, the o-CuTPPS4 does not “yellow” magenta dyes. Magenta compositions containing the o-CuTPPS4 result in a more “blue” magenta color.
The present invention is further directed to a process of making o-TPPS4 and o-CuTPPS4 by the following reaction:
The above process produces o-TPPS4 at yields of about 82%.
The reaction conditions for the above process may vary. Typically, the reaction may be carried out as follows. The reactants are purified by the following process or a similar purification process. The pyrrole is distilled under argon and a fraction is collected at 140° C. The 2-formylbenzenesulfonic acid, sodium salt is purified by a Dean and Stark method using benzene as the solvent. The solution is filtered at 60° C. and the solid pumped in a vacuum oven overnight at room-temperature. The p-toluene sulfonic acid may also be purified by a Dean and Stark method using benzene as the solvent.
The 2-formylbenzenesulfonic acid, sodium salt, N,N-dimethylformamide (DMF) and pyrrole are placed in a reaction vessel and stirred at room-temperature. The mixture is flushed with argon for about five minutes while stirring prior to heating. The mixture is then heated to 100° C. for about ten to twelve minutes. The toluene sulfonic acid dissolved in 15 ml of DMF is injected into the reaction mixture. The reaction mixture is heated to 150° C. and held at this temperature for about 50 minutes. The reaction mixture is then cooled in an ice bath for about 20 minutes and then poured into 1000 ml of benzene and stirred at room-temperature for about 10 minutes. The precipitate is filtered using a Buchner funnel and dried to produce a solid. The solid is then stirred in 500 ml of ethanol for about 30 minutes and filtered. The wet solid is pumped in a vacuum oven for about three hours to yield a finished product.
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