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April 14, 1884


The opinion of the court was delivered by: Blatchford, J.

E. N. Dickerson, for appellants.

B. F. Thurston, for appellee.

This is a suit in equity, brought in the circuit court of the United States for the Southern district of New York, by Badische Anilin & Soda Fabrik, a corporation organized under the laws of the grand duchy of Baden, in the empire of Germany, against the appellants, for the infringement of reissued letters patent No. 4,321, granted to Charles Graebe, of Frankfort on the Main, and Charles Liebermann, of Berlin, Prussia, April 4, 1871, for an 'improvement in dyes or coloring matter from anthracine.' The original patent, No. 95,465, was granted to the same persons, October 5, 1869, for an 'improved process of preparing alizarine.' It was reissued on two separate amended specifications, Division A and Division B. No. 4,321 is Division B.

The following is the text of the specifications of No. 4,321 and No. 95,465. Reading in it what is outside of brackets, and what is inside of brackets, omitting what is in italics, gives the specification of No. 4,321. Reading what is outside of brackets, including what is in italics, omitting what is inside of brackets, gives the specification of the original patent: 'Be it known, that we, Charles Graebe, of Frankfort on the Main, and Charles Liebermann, of Berlin, in the kingdom of Prussia, have invented a [new and useful improvement in the manufacture of alizarine;] process for preparing alizarine from anthracine; and we do hereby declare the following to be a full, clear, and exact description thereof, which will enable those skilled in the art to make and use the same. We first change the anthracine into anthrakinon (oxanthracine,) a substance known to [the] chemists by the investigations of Anderson. For this purpose we take one part, by weight, of anthracine, two and a half parts, by weight, of bichromate of [potash,] potassa, and ten or fifteen parts, by weight, of concentrated acetic acid, and we heat these substances together in a vessel, either of glass or clay, to about 100 deg. centigrade to 120 deg. centigrade, till nearly all of the bichromate of [potash] potassa is dissolved and the liquid has acquired a deep green color. We then recover the acetic acid not consumed in the reaction by distillation, and treat the residuum with water to remove the chromic acetate. From the insoluble mass we obtain the anthrakinon in a pure state by distilling the whole from a retort of glass or iron. In the place of the acetic acid, sulphuric acid, diluted with one or two parts of water, may be employed. Instead of the method just described, we also employ the following one: We heat the anthracine in a vessel of glass or of clay, with ten parts of concentrated acetic acid, to about 100 deg. centigrade, or a little higher, and we add nitric acid of about 1.3 specific gravity, in small portions, till the violent reaction ceases. After distillation of the acetic acid we purify the residuum, as before. We then convert the anthrakinon, prepared by one of the methods described, into bibromanthrakinon. For this purpose we take three parts of anthrakinon, five parts of bromine, and we heat these substances for ten or twelve hours, or until nearly the whole of the bromine has disappeared, to a temperature, by preference, of about 100 deg. centigrade, in a suitable close vessel, either of glass or enameled or glazed iron, which is capable of sustaining the pressure [which is] generated by the reaction. The apparatus is then allowed to cool. It is opened in order to permit the escape of [bromic] hydrobromic acid, which can be recovered by absorption either in water or in an alkaline solution. We purify the bibromanthrakinon remaining in the vessel, as a solid substance, by crystallization from benzole. Instead of the method above described for preparing bibromanthrakinon, we also employ the following: We convert first the anthracine into a bromine derivative, into the tetrabromanthracine, known to chemists by the investigations of Anderson. We take one part of this tetrabromanthracine, and we heat it in a retort of glass or clay with about five parts of nitric acid of about 1.3 specific gravity to 100 deg. centigrade, as long as vapors of bromine are evolved. We distill off the greater portion of the nitric acid, wash the residuum with water, and purify it by crystallization from benzole. We thus receive the bibromanthrakinon as before, in the form of a yellow, solid mass. We then convert the bibromanthrakinon into alizarine. For this purpose we take one part of bibromanthrakinon, two to three parts of caustic potash or soda, and so much water as is necessary to dissolve the alkali, and we heat the whole in an open vessel of glass, glazed or enameled iron, or silver, to about 180 deg. to 260 deg. centigrade for one hour, or [till] until the mass has acquired a deep blue color. We then dissolve it in water and filter the violet solution, from which we precipitate the alizarine by an inorganic or organic acid. We collect the yellow flocks of alizarine thus obtained on a filter and wash them with water. By these methods we receive the alizarine in a form in which it can be employed in the same manner as the different preparations from madder. In the place of bromine, chlorine [also] may also be employed, but not so conveniently, as the reactions above described are more difficult to accomplish with chlorine than with bromine. Having thus described the nature of our invention and the manner of performing and carrying out the same, we would have it understood that we do not confine ourselves to the exact details hereinbefore given.'

The claim of No. 4,321 is as follows: 'Artificial alizarine, produced from anthracine or its derivatives by either of the methods herein described, or by any other method which will produce a like result.' The claim of the original patent was in these words: 'The within-described process for the production of alizarine, by first preparing bibromanthrakinon or bichloranthrakinon, and then converting these substances into alizarine, substantially as above set forth.'

The bill of complaint alleges that No. 4,321 was issued 'for a distinct and separate part of the same invention, on a corrected specification,' on the surrender of No. 95,465; and No. 4,321 states, on its face, that, on such surrender, new letters were ordered to issue 'on two separate amended specifications.' But Division A, No. 4,320, is not in the record before us. The bill alleges the infringement to have been committed by making, selling, or using the invention or dyes containing it. The answer denies the manufacture of alizarine, but avers that the defendants have sold in the United States alizarine lawfully made in Germany, and imported as an article of commerce, which was not made by the process described in No. 4,321, or any proces substantially the same, but was made according to processes which were invented subsequently to the date of No. 95,465, and are the subject of different and independent letters patent. The answer also avers 'that alizarine is a natural product, having a well-known definite constitution; that it is not a composition of matter, within the meaning of the statute, but has been well known in the arts, from time immemorial, for the purpose of dyeing, and has generally been extracted from 'madder root,' and from other analogous products, by various processes suitable for that purpose; that, therefore, there can be no valid patent granted for alizarine; and that No. 4,321 is void.' The answer refers to 'Watts' Chemical Dictionary, published before 1869, under the title 'Alizarine,' to show that alizarine was well known long before the said patent;' and also sets up that the patent had expired because prior patents granted to the patentees in foreign countries, for the same invention, had expired. Proofs were taken, and, on final hearing, the circuit court decreed that No. 4,321 was valid, and had been infringed, and ordered a reference as to profits and damages, and a perpetual injunction against the making, using, or selling of the article designated in No. 4,321 'artificial alizarine,' or dyes containing the invention described in and secured by No. 4,321. Afterwards, there was a final decree against the defendants for $13,326.65 and costs, of which $12,871.86 was for profits made by the defendants, 'by the sale of artificial alizarine, in infringement' of No. 4,321. From this decree the defendants have appealed.

This reissued patent No. 4,321 had been adjudicated in the circuit courts in several cases. It was before the circuit court in Massachusetts, in February, 1878, and the decision of Judge SHEPLEY is in Badische Anilin & Soda Fabrik v. Hamilton Manuf'g Co. 3 Bann. & A. 235, and 13 O. G. 273. It was also before the circuit court for the Southern district of New York, in September, 1878, and the decision of Judge WHEELER is in Badische Anilin & Soda Fabrik v. Higgin, 15 Blatchf. C. C. 290, and 3 Bann. & A. 462, and 14 O. G. 414. The decision of Judge WHEELER in the present case, in April, 1879, is in 16 Blatchf. C. C. 155, and in 4 Bann. & A. 215. The patent was also before the circuit court in Massachusetts, in September, 1879, and the decision of Judge LOWELL is in Badische Anilin & Soda Fabrik v. Cummins, 4 Bann. & A. 489. In all of these cases the validity of No. 4,321 was sustained.

In the case before Judge SHEPLEY, it was held that No. 4,321 was a valid patent for a manufacture and composition of matter, an artificial dye-stuff, called artificial alizarine, being a new product, produced by a new process, not a chemically pure alizarine, but having combined with the alizarine in it, anthrapurpurine, isopurpurine and other bodies, not known to have existed before they were produced by Graebe and Liebermann, the presence of some of which bodies appeared to much enhance the value of the dye-stuff. It was decided that the defendants had used that article.

In the case against Higgin, it was held that the product of the process described in No. 4,321 contains isopurpurine, anthrapurpurine, monoxanthraquinone and other ingredients, which were not only not ingredients in pure alizarine or madder alizarine, but did not exist in any dye-stuff with chemically pure alizarine, C14 H8 O4, before that of Graebe and Liebermann, and are useful coloring agents, so that the product invented is a new composition of matter. It was decided that the defendants had used or sold dye-stuffs substantially the same, though claimed to be the product of a different process.
In the present case, it was insisted in the circuit court, by the defendants, that the patented product was the same thing as the natural dye-stuff, alizarine, found in the root of the madder plant, and chemically known by the formula C14 H8 O4, and not patentable. But it was decided that the article which Graebe and Liebermann had made synthetically from anthracine, though having the same chemical formula as madder alizarine, was essentially different, in capabilities and properties, from chemically pure alizarine, madder alizarine, or any coloring matter before known; that the article dealt in by the defendants was produced by the process of United States letters patent No. 154,536, granted July 28, 1874, to Heinrich Caro, Charles Graebe, and Charles Liebermann; that the use of sulphuric acid, in the process of the latter patent, performs the same office, in the same way, as the bromine in the process of No. 4,321; and that the products of the two processes are identical.

In the case before Judge LOWELL, he held that what Graebe and Liebermann sought to discover, and supposed they had discovered, was the alizarine which is the dye-stuff of madder; that what is called 'artificial alizarine' contains important dyeing substances not found in madder, namely, anthrapurpurine and isopurpurine (accordingly as these may be two substances or one and the same substance) and flavopurpurine, which substances produce valuable effects not produced by any extracts from madder; that, although the defendant insisted that those new purpurines were not found in the artificial alizarine made by the bromine process of No. 4,321, and were found only in artificial alizarine made by methods in vented since Graebe and Liebermann invented that process, and the evidence on that point was in much conflict, yet it was shown that pure alizarine, pure isopurpurine, and pure flayopurpurine were all contained in the patented article; that the artificial alizarine of No. 4,321 is different in some important respects from any article known before; that the new article of manufacture claimed in No. 4,321 was new in fact; and that the infringement was made out.

In Watt's Dictionary of Chemistry, vol. 1, p. 113, published in 1866, Alizarin is stated to be a red coloring matter obtained from madder, first prepared by Robiquet and Colin. This was in 1826. The correct formula of alizarine, C14 H 8 O4, was first arrived at by Strecker, in 1866. It means that there are 14 atoms of carbon, 8 atoms of hydrogen, and 4 atoms of oxygen in each molecule. At this stage, Graebe and Liebermann took up the subject and treated madder alizarine with the view of determining what was its mother substance. They tell the story themselves, in a paper in the record, entitled 'Artificial Alizarine,' which is a translation from the original, prepared in German by them, contained in the Official Report of the Vienna Exhibition of 1873, and also published separately in 1876. They heated madder alizarine with zinc dust, and made the alizarine give up its four atoms of oxygen, and take up two atoms more of hydrogen. They thus obtained a hydro-carbon, identical with that found in coal-tar, called anthracine and having the formula C14 H10. They then conceived the idea of converting anthracine into alizarine. Anthracine was difficult to obtain, and the experiment was conducted on a small scale. But it resulted in the process, described in No. 4,321, of converting anthracine into anthrachinon, the formula of which was C14 H8 O2, and then heating the anthrachinon with bromine and obtaining bibromanthrachinon, and heating that with caustic potash or soda, and obtaining alizarine. Graebe and Liebermann thus solved the problem of the synthesis of alizarine. It was a matter of great scientific interest, and gave thus solved the problem of the that the first method, described in No. 4,321, for preparing the bibromanthrakinon was so laborious that they devised the other method described, of first converting anthracine into tetrabromanthracine, and then treating that with nitric acid to obtain bibromanthrakinon. 'This method,' they state, 'made it possible to obtain the alizarine more readily, and aroused hopes of its technical execution,' although it involved two more reactions than the first method.

In regard to the alizarine thus obtained, the same paper says: 'The artificial alizarine, besides having the same composition, had also the same properties as vegetable alizarine. In hydrated alkalies it is soluble, with a blue violet to purple color. The solutions of the alkali salts give, with lime, baryta, lead, iron, alumina, and tin salts, lakes corresponding to the madder lakes. Cloth printed with mordants dyes exactly alike with both coloring matters. From these salt-like compounds yellow floculent alizarine is set free by the addition of a mineral acid. The artificial coloring matter shows the same solubilities, and the solutions of the alkaline salts the same absorption spectra, which are known of the natural coloring matter. The free coloring matter sublimes in beautiful yellow to red needles, which cluster together like feathers. On oxidizing with nitric acid, phthalic acid and oxalic acid are formed. Heated with zinc dust, the artificial alizarine is again converted into anthracine.' The paper then proceeds: 'The above methods, which now, from a technical point of view, have only a historic interest,* and are, therefore, described without further detail, make up the subject of the patents taken out in England on the eighteenth of December, 1868, and then also in France, Prussia, most German states, Austria, Russia and America.'

The provisional specification deposited in the English patent-office, December 18, 1868, which was the date of the patent, gives a short description of the process and says: 'The alizarine prepared in this artificial way is perfectly pure, and can be employed in all the applications for which the different preparations of madder are used.' The full specification, filed June 17, 1869, is substantially identical with the specification of No. 95,465, and claims 'the artificial production of alizarine, by ...

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