DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Status of Claims
Claims 1 – 8 are pending.
Claims 1 – 8 are rejected.
Drawings
The drawings are objected to because the single Figure is not referenced according to the MPEP 1.84 (u) Numbering of views.
(1) The different views must be numbered in consecutive Arabic numerals, starting with 1, independent of the numbering of the sheets and, if possible, in the order in which they appear on the drawing sheet(s). Partial views intended to form one complete view, on one or several sheets, must be identified by the same number followed by a capital letter. View numbers must be preceded by the abbreviation "FIG." Where only a single view is used in an application to illustrate the claimed invention, it must not be numbered and the abbreviation "FIG." must not appear.
Amending the title of the drawing to “The Figure” will overcome this objection.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claim(s) 1-7 are rejected under 35 U.S.C. 103 as being unpatentable over Ke et al., (RSC Advances, 2015, pp. 22837 – 22840), in view of Yang et al. (Organic Letters, 2011, pp. 4340 - 4343), and further in view of Desouhant-Massacret (US 9,403,745) and Ryszard et al. (PL 192178; See English translation).
The rejected claims cover, inter alia, a method for producing salicylic acid comprising hydroxylation in which salicylic acid is produced by reacting 2-halogenated benzoic acid in an aqueous solvent at a reaction temperature of 155°C or higher and 300°C or lower in the presence of a copper source, a ligand, and a base.
Dependent claim 2 further limits the reaction pressure. Dependent claim 3 further limits the ligand. Dependent claim 4 further limits the copper. Dependent claims 5 and 6 further limit the purification adsorbent. Dependent claim 7 further limits the method. Dependent claim 8 further limits the product.
However, Ke discloses a simple and efficient protocol for microwave-assisted copper-catalyzed hydroxylation of aryl halides in water. (abstract, & Table 2). Ke discloses the hydroxylation of 2-idobenzoic acid to salicylic acid in water in the presence of Cucl2, an amine ligand L3 and a base at a reaction temperature of 120°C.
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56
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Table 1 L3 =
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46
72
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.
The difference between Ke and the instantly claimed invention is as follows: reaction temperature of 155° C or higher and 300° C or less; reaction pressure of 0.1MPa or more and 10 MPa or less; purification B salicylic acid produced is brought in contact with zeolite; salicylic acid produced is brought in contact with zeolite; purification A salicylic acid produced is brought in contact with a synthetic adsorbent; a flow synthesis reaction; and content of aromatic impurities in the produced salicylic acid.
However, with regard to the reaction temperature of 155° C or higher and 300° C or less, the Examiner turns to the teaching of Ke and Yang. In Ke Table 2 the reaction temperature is 120°C with a reaction time of 40 minutes. (pp. 22838). In Yang Scheme 3 discloses the reaction of copper-catalyzed conversion of aryl chlorides to phenols.
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166
470
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. Producing
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, where L5 is
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. However, according to Scheme 3, the reaction that produces 6g is conducted at a temperature of 150°C for 24 hours. Comparing Ke and Yang, it seems that an increase in temperature produces an increase in product yield in combination with time. (pp. 4342)
In light of the teachings of this regards the Examiner considers Applicant’s examples. The application states that the salicylic acid (SA) can be obtained with high selectivity and high productivity in a short reaction time by setting the reaction temperature from 155°C to 300°C (par. [0160]). However, the only tentatively demonstrated effect is that for the range of temperatures 180-210°C a higher %area is obtained (table 7). In this context it is noted that there are no suitable comparative example proving that this effect is due to the temperature only.
For instance, in Applicant’s Example 18 (165°C) the %area of SA is 25.61%, in example 17 (temperature 200°C) the %area of SA is 35.68%, which is less than for the comparative example 6 (temperature 140°C). It can therefore be concluded that the temperature %area of SA is dependent on the combination of at least reaction temperature and reaction time.
Therefore, based on the teachings of the prior and in view of Applicants results in their Examples; the temperature differences between the claimed invention and the prior art can be affected via routine experimentation by the ordinary artesian skilled in the art. When the general condition of a claim are disclosed in the prior art, it is not inventive to discover optimum of workable ranges by routine experimentation. In re Aller, 220 F.2nd 454, 456, 105 USPQ 233, 235 (CCPA 1955).
Regarding the reaction pressure of 0.1MPa or more and 10 MPa or less, the Examiner turns to the teaching of Ke. The prior art of Ke does not highlight a reaction pressure. However, one of ordinary skill in the art at the time of the instantly claimed invention, when viewing Ke would reasonably presume that the reaction takes place at standard atmospheric pressure. Standard atmospheric pressure is 0.1 MPa. As such, the pressure as set out in claim 2 is disclosed.
It is noted that a prima facie case of obviousness has been established when the reference discloses all the limitations of a claim except for a property and the examiner cannot determine whether or not the reference inherently possesses properties that render obvious the claimed invention but has a basis for shifting the burden of proof to applicant, as per In re Fitzgerald, 619 F.2d 67,205 USPQ 594 (CCPA 1980). See also In re Best, 195 USPQ 430,433 (CCPA 1977) as to the providing of this rejection under 35 USC 103 in addition to the rejection made above under 35 USC 102.
Regarding purification B salicylic acid produced is brought in contact with zeolite; salicylic acid produced is brought in contact with zeolite, the Examiner turns to the teaching of Desouhant-Massacret. The prior art of Desouhant-Massacret discloses a method for separating salified phenolic compounds. (abstract) In Desouhant-Massacret adsorption involves separating the phenolic compound form the aqueous reaction mixture with an adsorbent. Zeolite is used because it can be easily regenerated. (pp. 5, ln 40 – 43, ln17 – 19 & 13 – 15). In Desouhant-Massacret, it is preferred to employ zeolites having two-dimensional or three-dimensional network. (pp. 7, ln 53 – 55).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the instantly claimed invention to subject crude product of Ke to a purification step wherein zeolite as suggested by Desouhant-Massacret is used. An implicit motivation to combine exists not only when a suggestion may be gleaned from the prior art as a whole, but when the improvement’ is technology-independent and the combination of references results in a product or process that is more desirable, for example because it is stronger, cheaper, cleaner, faster, lighter, smaller, more durable, or more efficient. Because the desire to enhance commercial opportunities by improving a product or process is universal-and even common-sensical, we have held that there exists in these situations a motivation to combine prior art references even absent any hint of suggestion in the references themselves. (DyStar Textilfarben GmbH & Co. Deutschland KG v. C.H. Patrick Co., 464 F.3d 1356, 1366, 1368; 80 USPQ2d 1641, 1649, 1651 (Fed. Cir. 2006)).
Therefore, all the claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination would have yielded predictable results to one of ordinary skill in the art before the effective filing date of the instantly claimed invention. KSR International Co. v. Teleflex Inc., 550 U.S. 398, 82 USPQ2d 1385 (U.S. 2007).
Regarding purification A salicylic acid produced is brought in contact with a synthetic adsorbent, the Examiner turns to the teaching of Ryszard. The prior art of Ryszard discloses a method for purifying crude salicylic acid, especially after its synthesis from phenol, using a cation exchanger in the form of a blocked functional group and a non-ionic non-polar or medium-polar sorbent and optionally a weakly or medium-basic ammonite in the chloride or sulfate form and after purifying the solution, salicylic acid is precipitated therefrom in a known manner. (abstract).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the instantly claimed invention to subject crude product of Ke to a purification step using a cation exchanger in the form of a blocked functional group and a non-ionic non-polar or medium-polar sorbent and optionally a weakly or medium-basic ammonite in the chloride or sulfate form as taught by Ryszard. An implicit motivation to combine exists not only when a suggestion may be gleaned from the prior art as a whole, but when the improvement’ is technology-independent and the combination of references results in a product or process that is more desirable, for example because it is stronger, cheaper, cleaner, faster, lighter, smaller, more durable, or more efficient. Because the desire to enhance commercial opportunities by improving a product or process is universal-and even common-sensical, we have held that there exists in these situations a motivation to combine prior art references even absent any hint of suggestion in the references themselves. (DyStar Textilfarben GmbH & Co. Deutschland KG v. C.H. Patrick Co., 464 F.3d 1356, 1366, 1368; 80 USPQ2d 1641, 1649, 1651 (Fed. Cir. 2006)).
Therefore, all the claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination would have yielded predictable results to one of ordinary skill in the art before the effective filing date of the instantly claimed invention. KSR International Co. v. Teleflex Inc., 550 U.S. 398, 82 USPQ2d 1385 (U.S. 2007).
With regard to a flow synthesis reaction, based on the teaching of Ke and Yang, in an actual industrial production, it is within the purview of one having ordinary skill in the art at the time of the instantly claimed to select such a reaction mode. This limitation is deemed to be obvious absent a showing of unexpected results.
A reference is good not only for what it teaches by direct anticipation but also for what one of ordinary skill in the art might reasonably infer from the teachings. (In re Opprecht 12 USPQ 2d 1235, 1236 (Fed Cir. 1989); In re Bode 193 USPQ 12 (CCPA) 1976). In light of the forgoing discussion, the Examiner concludes that the subject matter defined by the instant claims would have been obvious within the meaning of 35USC 103.
Claim Rejections - 35 USC § 103
Claim(s) 1, 6 and 8 are rejected under 35 U.S.C. 103 as being unpatentable over Ritter (US 7,358,391) in view of Ritter (7,335,791) (Ritter 2) and further in view of Gelmont et al. (Organic Process Research & Development, 2022, pp. 591 – 596) & Ryszard et al. (PL 192178; See English translation).
Rejected claim 1 is discussed in paragraph 9 above.
. Dependent claim 6 further limit the purification adsorbent. Dependent claim 8 further limits the product.
However, Ritter discloses a process for the preparation of salicylic acid comprising 10 mmol of 2-bromobenzoic acid was stirred with a solution of 12.5 mmol Na.sub.2CO.sub.3 in 10 mL H.sub.2O at 50-75.degree. C. until all of the 2-bromobenzoic acid was dissolved. Subsequently, 0.01 mmol CuSO.sub.4 and 0.04 mmol of ligand (valine, proline or N-methylanthranilic acid as indicated in Table 1), dissolved under stirring with air in 1 mL deionized water, were added; and the reaction mixture was heated at the temperature and for the different times as noted in Table 1. After cooling to ambient temperature, the reaction mixtures were acidified with 35% aqueous HCl. The products were isolated by filtration, washed with water and dried under vacuum. The crude reaction product was analyzed by .sup.1H NMR (d6-dmso). The results are summarized in Table 1. (pp. 10 Examples 1, 2, & Table 1(a) & 2(a)).
Additonally, Ritter 2 discloses a method for preparing salicylic acid comprising: 2.00 g (9.95 mmol) of 2-bromobenzoic acid was combined with 10 g of H.sub.2O. 1.11 g (10.45 mmol) of Na.sub.2CO.sub.3 was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Another 1.58 g (14.92 mmol) of Na.sub.2CO.sub.3 was added to the reaction mixture and reflux was continued for 30 min. Separately, 22 mg of CuBr.sub.2 and 28 mg of rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F) were combined with 2 mL H.sub.2O under nitrogen to give a deep purple solution. This solution was added to the stirred reaction mixture via syringe at 80.degree. C. under nitrogen and stirred for 1 h at 80.degree. C. After cooling to 25.degree. C., the reaction mixture was acidified with 15% HCl, producing a white precipitate. The white precipitate was filtered and washed with water. After drying, a total of 1.34 g (9.7 mmol, 98% yield) salicylic acid was collected. The purity was determined by .sup.1H NMR to be about 99%.(pp. 18, Example 1)
The difference between Ritter, Ritter 2 and the instantly claimed invention is as follows: reaction temperature of 155° C or higher and 300° C or less; purification A salicylic acid produced is brought in contact with a synthetic adsorbent; and content of aromatic impurities in the produced salicylic acid.
Regarding the reaction temperature of 155° C or higher and 300° C or less, the Examiner turns to the teaching of Ritter, Ritter 2 and Gelmont. A problem to be solved by Applicant’s claim 1 is to provide stable production at low cost with high productivity. The Examples of Ritter and Ritter 2 demonstrate that they solve the same problem without using higher reaction temperatures. However, Ritter and Ritter 2 acknowledge that various prior art processes for the preparation of hydroxybenzoic acid are characterized by long reaction times and limited conversion, resulting in a significant decrease in productivity, or requires pressure and/or higher temperature (typically 140 to 250 ° C), to obtain better rate and productivity; that is, for such reaction processes in which a copper-containing catalyst catalyzes the hydrolysis of halobenzoic acid to produce hydroxybenzoic acid, there are prior art reactions at higher reaction temperatures, such as 140 to 250 ° C, and good rates and productivities arc obtained by the higher reaction temperatures. (Ritter col. 1, ln 62 – 66 & Ritter 2 col. 1, ln 62 – 66). An example is shown in Gelmont, wherein that process at a temperature of 100 to 270 ° C, in an aqueous alkaline solution, in the presence of a copper catalyst, by hydrolysis of 5-bromoisophthalic acid and mixtures of 5-bromoisophlhalic acid, dibromoisophlhalic acid isomers and salts thereof prepare 5-hydroxybromoisophthalic acid. (pp, 493 rt. col. “Preparation of Crude 5-HIPA to pp. 594 rt col. Table 4).
Also, even with these teachings, it is generally known by one skilled in the art, that for most organic reactions, increasing the reaction temperature tends to result in higher reaction rates. Although very high yields and product purities have been obtained in the technical solutions disclosed in Ritter or Ritter 2, it is still motivated by the person skilled in the art to further shorten the reaction time, i.e. To increase the reaction efficiency, to achieve it by means of a method of increasing the reaction temperature and to determine the appropriate temperature range by limited trials.
As such, when considering the prior art teachings, the solution of Applicant’s claim 1 have no outstanding substantial features and significant advancement. Therefore, based on the teachings of the prior and in view of Applicants results in their Examples; the temperature differences between the claimed invention and the prior art can be affected via routine experimentation by the ordinary artesian skilled in the art. When the general condition of a claim are disclosed in the prior art, it is not inventive to discover optimum of workable ranges by routine experimentation. In re Aller, 220 F.2nd 454, 456, 105 USPQ 233, 235 (CCPA 1955).
Regarding purification A salicylic acid produced is brought in contact with a synthetic adsorbent (claim 6), the Examiner turns to the teaching of Ryszard. The prior art of Ryszard discloses a method for purifying crude salicylic acid, especially after its synthesis from phenol, using a cation exchanger in the form of a blocked functional group and a non-ionic non-polar or medium-polar sorbent and optionally a weakly or medium-basic ammonite in the chloride or sulfate form and after purifying the solution, salicylic acid is precipitated therefrom in a known manner. (abstract).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the instantly claimed invention to subject crude product of Ritter or Ritter 2 to a purification step using a cation exchanger in the form of a blocked functional group and a non-ionic non-polar or medium-polar sorbent and optionally a weakly or medium-basic ammonite in the chloride or sulfate form as taught by Ryszard. An implicit motivation to combine exists not only when a suggestion may be gleaned from the prior art as a whole, but when the improvement’ is technology-independent and the combination of references results in a product or process that is more desirable, for example because it is stronger, cheaper, cleaner, faster, lighter, smaller, more durable, or more efficient. Because the desire to enhance commercial opportunities by improving a product or process is universal-and even common-sensical, we have held that there exists in these situations a motivation to combine prior art references even absent any hint of suggestion in the references themselves. (DyStar Textilfarben GmbH & Co. Deutschland KG v. C.H. Patrick Co., 464 F.3d 1356, 1366, 1368; 80 USPQ2d 1641, 1649, 1651 (Fed. Cir. 2006)).
Therefore, all the claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination would have yielded predictable results to one of ordinary skill in the art before the effective filing date of the instantly claimed invention. KSR International Co. v. Teleflex Inc., 550 U.S. 398, 82 USPQ2d 1385 (U.S. 2007).
With regard to the content of aromatic impurities in the produced salicylic acid (claim 8) , the Examiner turns to the teaching of Ritter and Ritter 2. The prior art of Ritter discloses a purty of more than 95% (Table1). Ritter 2 discloses a purity of more than 95% (Example 1 & Example 2, Table 3). Ritter and Ritter 2 do not provide the type and content of impurities; but, based on the purity levels obtained would fall within the range of 0.5% or less. Additionally, the exact type and content of the impurities in the reaction product can easily be determined by routine experimentation of a person of ordinary skill in the art before the effective filing date of the instantly claimed invention. Where the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
Art Made of Record
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. Jia, et al. (CuI-catalyzed hydroxylation of aryl bromides under the assistance of 5-bromo-2-(1H-imidazol-2-yl)pyridine and related ligands, Tetrahedron Letters, 52, 2011, pp. 5593 – 5595).
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to YATE' K. CUTLIFF whose telephone number is (571)272-9067. The examiner can normally be reached Monday-Friday (8:30 - 5:30).
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Scarlett Y. Goon can be reached at (571) 270-5241. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/YATE' K CUTLIFF/Primary Examiner, Art Unit 1692
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