Archive for the ‘intellectual property’ tag
Ecolochem, Inc. v. Southern California Edison Co. - Case Brief
Ecolochem, Inc. v. Southern California Edison Co., 227 F.3d 1361 (Fed. Cir. 2000).
Facts:
Ecolochem owned two patents directed to methods of demineralization and deoxygenation of water. Ecolochem developed the underlying technology while contracting its water purification and supply services to Southern California Edison Company. Edison at the time was constructing its own water purification facility. Ecolochem filed suit against Edison upon completion of the project, alleging that Edison’s facility infringed Ecolochem’s patents. The district court granted partial summary judgment in favor of Edison and held that the claims of the two patents were invalid as either anticipated or obvious.
On appeal, the Court of Appeals for the Federal Circuit reversed and remanded for retrial, holding that disputed issues of material fact remained pertaining to evidence of secondary indicia of nonobviousness presented by Ecolochem.
Following a bench trial on remand, the district court found that Edison had willfully infringed Ecolochem’s patents. The court also found, however, that the infringed claims were invalid as obvious in light of a combination of prior art including references that taught the use of mixed-bed ion exchange resins. Ecolochem appealed the finding of invalidity regarding the claims of the ‘411 patent but did not assert the other patent on appeal.
Issues:
1. Whether process patent claims are anticipated by prior art articles or by a scientist’s public presentation if the entire process is not fully described in any one reference.
2. Whether an invention that combines two known elements is obvious when nothing in the prior art as a whole suggests, teaches, or motivates one of ordinary skill in the art to make the combination.
3. Whether evidence of secondary considerations can rebut a prima facie case of obviousness and raise a genuine issue of fact that requires a remand for trial of the issue.
Holding:
1. No. Prior art references that do not expressly teach each and every element of the process described in a patent do not anticipate the patent.
2. No. Obviousness cannot be established by combining the teachings of the prior art unless the prior art contains a teaching, suggestion or motivation to combine.
3. Yes. Evidence of secondary indicia of nonobviousness may raise a material issue of fact necessitating a remand for trial on the issue.
Discussion:
The Court of Appeals for the Federal Circuit reviewed de novo the district court’s finding that the claims were obvious and invalid. The court noted that the prior art taught the use of hydrogen to deoxygenate water but did not teach the deoxygenation of water using hydrazine with mixed-bed ion exchange resins. With the exception of claim 20, the court reversed the district court’s finding that Ecolochem’s claims were anticipated by a scientist’s public presentation because a key part of the claimed process had been omitted from the presentation. The court found that the presentation included every limitation of claim 20 and affirmed the district court’s finding of invalidity regarding that claim.
The court held that the combination of two prior art references does not render patent claims obvious absent a teaching, suggestion, or motivation to combine the information and where there was evidence of teaching away in the prior art. Here, the court held that the prior art taught away from the mixed-bed ion exchange process and that the claims were therefore not obvious in light of secondary indicia of nonobviousness.
The Federal Circuit considered evidence of secondary indicia of nonobviousness offered by Ecolochem to overcome a prima facie showing of obviousness for claim 20 and affirmed the district court’s determination that the claim was obvious. The court reasoned that the lack of evidence of copying by others in addition to evidence that showed that Ecolochem’s process was not developed in response to a “long felt need” pointed more strongly toward a finding of obviousness than commercial success and teaching away supported the opposite conclusion.
Disposition:
Affirmed with regard to the district court’s finding that claim 20 was invalid, reversed with respect to all of the other claims, and remanded for a determination of damages to Ecolochem for infringement of the remaining valid claims.
Tags: anticipation, Cases, Cases, court, fpost, intellectual property, law, lawsuit, litigation, obviousness, Patent, trial, TSM testEpoxy Derivatives
2,794,028 Patented May 28, 1957
EPOXY DERIVATIVES
Benjamin Phillips and Paul S. Starcher, Charleston, W. Va., assignors to Union Carbide and Carbon Corporation, a corporation of New York
No Drawing. Application August 13, 1953, Serial No. 374,141
3 Claims. (Cl. 260— 348)
This invention relates to new organic compounds and has for an object the provision of new types of organic compounds suitable for use in the plastics and resins industry, as well as other important industrial uses. More particularly, this invention relates to epoxy compounds prepared from tetrahydrophthalic anhydride and tetrahydrophthalic acid.
The new compounds of this invention are useful as modifiers for various condensation resins and as plasticizers and stabilizers for various synthetic resins.
The epoxides obtained by the epoxidation of the tetrahydrophthalic acid and its derivatives are particularly attractive, in view of the fact that they are potentially low cost chemicals since the tetrahydrophthalic anhydride is readily obtained by the reaction of butadiene and maleic anhydride, both of which are commercially available in large quantities.
More specifically, the compounds which comprise this invention are useful as chemical intermediates in preparing a large number of chemical compounds by virtue of their reactive epoxide group which can be reacted with a large number of compounds having a labile hydrogen atom.
The compounds of this invention may be conveniently illustrated by the following structural formula:
[see figure]
The compounds of this invention are produced by the oxidation of the olefinic linkage contained in the starting material, as in the oxidation of the tetrahydrophthalic anhydride to yield the 4,5-epoxycyclohexane-l,2-dicarboxylic anhydride otherwise known as 7-oxabicyclo-[4.1.0]heptane-3,4-dicarboxylic anhydride.
The oxidizing agents employed in the production of these new compounds are the peracids, such as, for example, peracetic acid, perpropionic acid, perbenzoic acid and the like. More particularly, peracetic acid is employed as the oxidizing agent to produce these epoxy compounds.
The use of the peracids to obtain certain beneficial oxidation results is not new in the art of oxidizing organic compounds. In fact, the history of the peracids dates back to the work of Baeyer and Villiger, who, in 1900, were able to prepare perbenzoic acid by the saponification of dibenzoyl peroxide. The tremendous interest displayed over the peracids is due to the fact that the peracids occupy somewhat a unique position as oxidizing agents. The peracids have the ability to effect several specific chemical transformations with very high efficiencies, whereas, other well known oxidizing agents, such as, for example potassium permanganate, have no such ability.
Among the most interesting types of chemical transformations peculiar to the peracids is that type of reaction which makes available the compounds of this invention, that is, the oxidation of unsaturated organic compounds to yield the corresponding epoxides. It is this particular oxidation ability of the peracids that makes available a host of chemical compounds that may have previously been produced only through laborious and tedious means and in minute quantities or were never heretofore obtainable. For purposes of illustration, the reaction whereby the epoxide derivative of tetrahydrophthalic anhydride is produced in accordance with our invention, may be written as follows:
[see figure]
The following examples will serve to illustrate the practice of the invention:
EXAMPLE I
Preparation of 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylic acid
Fifty grams of tetrahydrophthalic acid was dissolved in 150 grams of acetone and the mixture was heated to 40° C. To this mixture was added 132 grams of a 25.4% solution of peracetic acid in acetone over a period of 40 minutes. The reaction mixture was heated at 40° C. for an additional six hours. To 100 grams of this reaction mixture was added enough petroleum ether to cause layer separation. The lower layer was recovered and titrated with petroleum ether until crystallization occurred. The crystals, after being washed with petroleum ether and dried weighed 11.1 grams. An analysis for epoxide content by the hydrogen bromide method indicated a purity of 64.2% calculated as 7-oxabicyclo-[4.1.0]heptane-3,4-dicarboxylic acid. The rest of the original reaction mixture was placed in a brine bath at —50° C. for eight days. The crystalline phase which separated, was filtered off, washed several times with petroleum ether, and dried. It weighed 7 grams. An analysis for epoxide groups by the hydrogen bromide method indicated a purity of 75.5% calculated as the epoxy acid. Titration of the acid groups followed by saponification, indicated that 82% of the theoretical carboxyl groups were still available. The product melted with foaming at 145°-150° C.
EXAMPLE II
Preparation of 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylic anhydride
One mol of tetrahydrophthalic anhydride was dissolved in 900 grams of ethylbenzene. One and one-half mols of a 23.4% peracetic acid solution in ethyl acetate was added to the anhydride solution over a period of two hours at a temperature of approximately 30° C. The reaction mixture was allowed to stand over night. White crystals of the reaction product was separated from the solution. This crude product had a melting point in the range 141°-143° C. and upon further purification, by two recrystallizations from dioxane, gave 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylic anhydride having the following properties:
[see figure]
What is claimed is:
1. An epoxide selected from the group consisting of 4,5-epoxycyc1ohexane-1,2-dicarboxylic acid and 4,5-epoxycyc1ohexane-l,2-dicarboxylic anhydride.
2. As a new epoxide, 4,5-epoxycyc1ohexane-l,2-dicarboxylic acid.
3. As a new epoxide, 4,5-epoxycyc1ohexane-l,2-dicarboxylic anhydride.
References Cited in the file of this patent
UNITED STATES PATENTS
2,550,494 Olin Apr. 24, 1951
2,570,029 Fluchaire Oct. 2, 1951
OTHER REFERENCES
Ziegler et al.: Annalen, vol. 551, pp. 17-18 (1942).
Gill: J. Chem. Soc., 1952: 4630-4632.
US patent 2794028 full text in PDF format
Tags: chemistry, epoxy, Historic Patents, intellectual property, invention, law, Patent, science10-Acyl Derivatives Of Apoyohimbine
United States Patent Office.
3,120,529
Patented Feb. 4, 1964
10-ACYL DERIVATIVES OF APOYOHIMBINE AND PROCESS THEREFOR
John Shavel, Jr., Mendham, N.J., assignor to Warner-Lambert Pharmaceutical Company, Morris Plains, N.J., a corporation of Delaware
No Drawing. Filed Feb. 10, 1961, Ser. No. 88,307
4 Claims. (Cl. 260—287)
The present invention relates to new and novel 10-acyl derivatives of apoyohimbine of the formula:
[see figure]
wherein R is the acyl radical of an aliphatic carboxylic acid containing 1 to 6 carbon atoms and to the non-toxic acid addition and quaternary ammonium salts thereof. This invention also relates to a method of producing these compounds.
The compounds of this invention are derivatives of the alkaloid apoyohimbine of the yohimbane series. They have interesting pharmacological activity and are useful as analgesics, tranquilizers and hypotensive agents. In addition, they are valuable intermediates in the production of other compounds of the yohimbane series. Included within the scope of this invention are such 10-acyl derivatives of apoyohimbine as 10-acetylapoyohmibine, 10-propionylapoyobimbine, 10-butyrylapoyohimbine, 10-valerylapoyohimbine and the like.
It has now been found that the compounds of my invention of the above formula may be prepared by treating the known apoyohimbine at between +25° C. and — 40° C. with an acid anhydride or acyl halide having R acyl groups in the presence of a Friedel-Crafts catalyst. The reaction is one of acylation with an R acyl group being substituted at the 10-position of the apoyohimbine starting material. The reaction is carried out in the liquid phase under anhydrous conditions in the presence of a Friedel-Crafts catalyst such as boron trifluoride, aluminum chloride, aluminum bromide, stannic chloride, ferric chloride, ferric bromide, hydrofluoric acid, polyphosphoric acid, titanium tetrachloride, sulfuric acid and the like, with boron trifluoride being particularly effective. The reaction mixture may also contain a carboxylic acid or a carboxylic acid ester corresponding to the acid halide or acid anhydride, that is, a carboxylic acid of the formula ROH, or an ester of the formula ROR1, wherein R1 is a lower alkyl group.
In carrying out the reaction the acylating agent (acid anhydride or acyl halide), either with, or without the corresponding acid or ester, is initially saturated with catalyst at a temperature between about —20° C. and + 10° C. The temperature of the mixture is then adjusted to the desired reaction temperature and the apoyohimbine starting material is added, either as a solid or as a solution in the acylating agent or in an inert organic solvent, such as rnethylene chloride, dioxan, tetrahydrofuran and the like. The reaction mixture is then stirred at the reaction temperature to completion and the product is recovered therefrom by conventional techniques of extraction, crystallization and chromatography.
It is to be understood that the new and novel compounds of this invention may be used as the free base or may be converted into the corresponding pharmaceutically acceptable non-toxic acid addition and quaternary ammonium salts. Exemplary of non-toxic acid addition salts are those formed with maleic, fumaric, benzoic, ascorbic, succinic, bismethylensalicylic, methylsulfonic, ethanedisulfonic, acetic, propionic, tartaric, salicyclic, citric, gluconic, lactic, malic, mandelic, cinnamic, citraconic, stearic, palmitic, itaconic, glyolic, benzenesulfonic, hydrochloric, hydrobromic, sulfuric, sulfamic, phosphoric and nitric acids. The acid addition salts may be prepared in the conventional manner, for example, by treating a solution or suspension of the free base in an organic solvent with the desired acid, and then recovering the salt which forms by crystallization techniques. The quaternary salts are prepared by heating a suspension of the base in a suitable solvent with a reactive alkyl halide such as methyl iodide, ethyl bromide, n-hexyl bromide, benzyl chloride or a reactive ester such as methyl sulfate, ethyl sulfate or methyl p-toluene sulfonate.
For therapeutic use, the new and novel compounds of this invention, as the free base, or as their acid addition or quaternary ammonium salts, may be formulated with conventional pharmaceutical carriers into dosage unit forms, such as tablets, capsules, elixirs, suppositories, solution, suspensions and the like. The following example is included in order further to illustrate the present invention:
Example
45 A mixture of 25 ml. glacial acetic acid and 150 ml. acetic anhydride is saturated with boron trifluoride at —10° C. by passing boron trifluoride into the solution for 15 minutes. The resulting mixture is cooled to —20° C. and 25 g. apoyohimbine are added. The reaction mixture is agitated for two hours and then is poured onto crushed ice. The suspension formed is made basic with ammonium hydroxide and extracted with chloroform. The extract is dried over sodium sulfate, filtered and evaporated to dryness. The residue, an oil, is crystallized from methanol to yield 19.9 g. of crystals, which on two further recrystallizations from methanol yield pure 10-acetylapoyohimbine (as the hydrate), M.P. 204-206° C. (dec.), [α]D25 +38° (pyridine, c.= l.l).
Analysis.—Calc.: C, 69.67; H, 7.12; N, 7.07. Found: 60 C, 69.73; H, 7.43; N, 7.35. It is understood that the foregoing detailed description is given merely by way of illustration and that many variations may be made therein without departing from the spirit of my invention.
Having described my invention, what I desire to secure by Letters Patent is:
1. A member selected from the group consisting of compounds of the formula:
[see figure]
wherein R is the acyl radical of an unsubstituted saturated aliphatic carboxylic acid of 1 to 6 carbon atoms and the pharmaceutically acceptable non-toxic acid addition and quaternary ammonium salts thereof with a compound selected from the group consisting of methyl iodide, ethyl bromide, n-hexyl bromide, benzyl chloride, methyl sulfate, ethyl sulfate and methyl p-toluene sulfonate.
2. 10-acetylapoyohimbine.
3. A method of preparing a compound of the formula:
[see figure]
wherein R is the acyl radical of an unsubstituted saturated aliphatic carboxylic acid of 1 to 6 carbon atoms which comprises treating apoyohimbine with a member selected from the group consisting of a carboxylic acid anhydride (R)2O and a carboxylic acid halide R—X wherein X is halogen and R has the meaning above at a temperature between +25° C. and —40° C. in the presence of a Friedel-Crafts catalyst.
4. A method according to claim 3 wherein said Friedel- Crafts catalyst is boron trifluoride.
No references cited.
PDF of United States Patent Number 3120529
Tags: chemistry, Historic Patents, Historic Patents, intellectual property, invention, law, organic chemistry, Patent, science, yohimbaneComposition Oil For Lubricating, Paint, &c.
UNITED STATES PATENT OFFICE.
WILLIAM H. SPOONER, OF BRISTOL, RHODE ISLAND.
COMPOSITION OIL FOR LUBRICATING, PAINT, &c.
Specification forming part of Letters Patent No. 45,090, dated November 15, 1864.
To all whom it may concern:
Be it known that I, WILLIAM H, SPOONER, of Bristol, in the county of Bristol and State of Rhode Island, have Invented certain new and useful Improvements in Composition Oils for Lubricating, Paint, and other Purposes; and I hereby declare that the following is a full, clear, and exact description of the same.
The object of this my invention is to produce a cheap substitute for the different oils or compositions of oils used in the arts for the purposes of lubricating, painting, softening wool, leather, &c. The large amount of mineral oil manufactured from coals, peat, tar, &c., or drawn from the oil-wells, and which can be afforded at comparatively small cost, suggested the employment of this substance as a substitute for animal or vegetable oil for the uses before mentioned, but it was found that it did not possess the requisite qualities.
Attempts were heretofore made to produce from coal-oil or paraffine lubricating or other dense oils used for various purposes in the arts. For this purpose caoutchouc or other gummy and resinous substances were combined with by dissolving them in coal-oil or paraffine; but the results do not appear to have given satisfaction, and no good lubricating, paint, or other like oil made from mineral oil or its distillates has, to my knowledge, been successfully introduced.
The experiments instituted by me have resulted in the production from mineral oils of an oil admirably adapted for lubricating machinery, oiling of wool, preparing paints, softening leather, and for many other purposes, and I have accomplished this by proceeding in the manner as follows: I first take caoutchouc or pure india-rubber, such as purchasable in the market, and dissolve it in paraffine-oil, benzine, or naphtha in the proportions of one pound of the former to four gallons of the latter. If paraffine-oil be used as the dissolving agent of caoutchouc, I would recommend that it should be warmed to about 100° Fahrenheit. The mixture of one pound of caoutchouc with four gallons of either of the above-named substances should be exposed to frequent agitation for about ten days, when the mixture will be complete and intimate. I then take paraffine-oil, such as derived from the distillation of coals, peat, tar, or petroleum, and add it to the mixture or solution before described in the proportions of forty gallons of the former to three of the latter, heating the mixture to a temperature of from 100° to 200° Fahrenheit, agitating the mass for five hours, more or less. The mixture is then allowed to rest, and a separation of impure and foreign matters and of undissolved caoutchouc will take place, when the clear oil, ready for use, may be drawn off.
Having thus fully described my invention and the manner in which the same is or may be carried into effect, I claim—
1. The method herein described of preparing oil adapted for use as a lubricating, paint, wool, currier’s, or other like oil by combining with dissolved caoutchouc paraffine-oil, when said combination is effected in the proportions and in the manner herein set forth.
2. As a new article of manufacture, a composition oil, the same consisting of caoutchouc dissolved in hydrocarbon mixed with the oily distillates of coal, peat, tar, or petroleum in the manner and the proportions set forth. In testimony whereof I have signed my name to this specification before two subscribing witnesses.
WILLIAM H. SPOONER.
Witnesses:
M. BENNETT,
JAS. E. FRENCH.
J.E.M. Ag Supply v. Pioneer Hi-Bred International - Case Brief
Facts:
Pioneer owned several patents directed to plants and seeds of new varieties of hybrid and inbred corn. When Pioneer sued J.E.M. for infringement, J.E.M. moved for summary judgment on the basis that sexually reproduced plants are not patentable subject matter under 35 U.S.C. § 101. Citing Diamond v. Chakrabarty, the district court denied J.E.M.’s motion and held that 35 U.S.C. § 101 covers plant life and that sexually reproducing plants are patentable subject matter. A unanimous panel of the Court of Appeals for the Federal Circuit affirmed the district court’s decision.
Issue:
Whether sexually reproduced plants and seeds are patentable subject matter within the scope of 35 U.S.C. § 101, despite being unpatentable under the later enacted and more specific Plant Variety Protection Act (PVPA).
Holding:
Yes. Plants are patentable subject matter under both the PVPA and 35 U.S.C. § 101.
Reasoning:
J.E.M. had argued that 35 USC § 101 did not apply to seeds and seed grown plants because Congress intended that they be protected under the Plant Protection Act of 1930 (PPA) and the (PVPA), and that the general statute was superseded by the more specific PVPA.
The Court held that Congress did not intend for the PVPA to exclude new plant varieties from protection under the patent statues. The court held that 35 USC and the PVPA differ in the rights and obligations imposed on a prospective patentee in order to obtain patent protection, but that plants are patentable subject matter under both.
Disposition: Affirmed.
Tags: Biotech, case, Cases, intellectual property, law, Patent, supreme court, utility