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 the Claims
The preliminary amendment filed on 04/23/2024 has been entered. Claims 1-11 have been amended; claims 12-15 have been canceled and claims 16-21 have been newly added. Thus claims 1-11 and 16-21 are currently pending and are under examination.
Claim Objections
Claim 9 is objected to because of the following informalities: correct “the step” in line 2 to “a step” because there is no earlier recitation of step (iii).
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 1-11 and 16-21 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 1 recites the limitation " the total molar amount of alkyl ester of levulinic acid supplied to the pressurized continuous flow reactor " in the last two lines. There is insufficient antecedent basis for this limitation in the claim because there is no earlier recitation of alkyl ester of levulinic acid supplied to the pressurized continuous flow reactor. The only agents supplied to the pressurized continuous flow reactor are furfuryl alcohol, aliphatic alcohol and protic acid, whereas the alkyl ester of levulinic acid is formed is formed in the resulting reaction mixture.
For purpose of applying art, the limitation will not be given patentable weight.
Claims 2-11 and 16-21 are also rendered indefinite for their dependency on claim 1.
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.
Claims 1-2, 4-6, 8, 10-11 and 16-21 are rejected under 35 U.S.C. 103 as being unpatentable over Parton (Parton, R. et al. Patent application publication number US2023/0322655A1; effectively filed on Aug. 14, 2020).
Regarding claim 1, 11, and 16-18, Parton teaches a process for forming an alkyl ester of levulinic acid or one or more reaction products thereof, said process comprising at least the following steps: (i) preparing or providing a first supply flux comprising furfuryl alcohol and aliphatic alcohol, and a second supply flux comprising at least one protic acid, wherein said protic acid is selected from the group consisting of sulfonic acid optionally selected from the group consisting of an alkyl-aromatic sulfonic acid, an aromatic sulfonic acid, a halosulfonic acid, and an aliphatic sulfonic acid; optionally, the sulfonic acid catalyst is p-toluenesulfonic acid or its monohydrate, 7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonic acid (camphor sulfonic acid) or methanesulfonic acid; or hydrates of each thereof, (ii) supplying the first supply flux and the second supply flux prepared or provided in step (i) to a pressurized continuous flow reactor system and contacting the first supply flux and the second supply flux in said pressurized continuous flow reactor system so that in the resulting reaction mixture alkyl ester of levulinic acid is formed by a protic acid-catalyzed reaction of furfuryl alcohol with said aliphatic alcohol, wherein the second supply flux supplies 0.032 mol of p-TSA (protic acid) and 2.05 mol of furfuryl alcohol (equivalent to 1.56*10−2 moles of p-TSA per mole of furfuryl alcohol) supplied by the first supply flux (Figs. 2-4, [0024], [0029], [0050], [0073], [0087]-[0091]).
Regarding claim 2, the aliphatic alcohol of the reference is selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol, n-pentanol, isopentanol, n-hexanol, n-octanol, n-decanol or 2-ethylhexan-1-ol ([0029]). Parton further exemplifies throughout the experimental data the formation of alkyl levulinate from the aforementioned aliphatic alcohols.
Regarding claims 4 and 19, the reference teaches that that the butyl levulinate yield (which would affect selectivity) increases with the residence time, the temperature (up to 140° C.), the molar ratio butanol/furfuryl alcohol, and the pTSA concentration ([0170]). The yield of butyl levulinate based on the residence time is as follows ([0209]):
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Furthermore, the reference teaches that CSTR runs at at least 90% conversion, more preferably 95% conversion more preferably 98% conversion of furfuryl alcohol ([0061]). Selectivity is calculated by yield/conversion and thus at conversion of 98%, experiments 8A-8E would have selectivities of about 92.1%, 91.4%, 87.5%, 91.1% and 88.3%, respectively.
Regarding claims 5 and 20-21, Parton teaches the concentration of furfuryl alcohol in the first CSTR, or in the reactor of the fed-batch set-up, is below 0.1 wt %, preferably below 0.01 wt % ([0065]); the reaction is carried out at temperatures between about 125 or 130 and 170° C ([0023]) and the residence time in the second reactor is in the range of 5 to 120 minutes ([0049]).
Regarding claim 6, no compound selected from the group consisting of compounds of Bi, Ga, Al, Sn and Fe, is present in the reaction mixture.
Regarding claim 8, non-reacted aliphatic alcohol is separated from the product flux leaving the pressurized continuous flow reactor system, and said non-reacted aliphatic alcohol is recycled to said pressurized continuous flow reactor system wherein alkyl ester of levulinic acid is formed by a protic acid-catalyzed reaction of furfuryl alcohol with said aliphatic alcohol ([0094]).
Regarding claim 10, in Parton, no compound selected from the group consisting of levulinic acid and alkyl esters of levulinic acid is supplied to the pressurized continuous flow reactor system.
Regarding claim 1, the difference between the claimed invention and Parton is that in the claim, 2.6*10−2 moles to 9*10-1 of protic acid per mole of furfuryl alcohol is supplied whereas in Parton 1.56*10−2 moles of protic acid per mole of furfuryl alcohol is supplied. In view of MPEP § 2144.05, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Thus, absent any showing of criticality or unexpected results, the instantly claimed mole of protic acid per mole of furfuryl alcohol is prima facie obvious over that of Parton.
It would thus have been prima facie obvious to a skilled artisan before the effective filing date of the instant invention to conduct a process for forming an alkyl ester of levulinic acid or one or more reaction products thereof, said process comprising at least the following steps (i) preparing or providing a first supply flux comprising furfuryl alcohol and aliphatic alcohol, and a second supply flux comprising at least one protic acid, wherein said protic acid is selected from the group consisting of sulfuric acid, halogen sulfonic acids, aliphatic sulfonic acids, aromatic sulfonic acids and alkyl-aromatic sulfonic acids, (ii) supplying the first supply flux and the second supply flux prepared or provided in step (i) to a pressurized continuous flow reactor system and contacting the first supply flux and the second supply flux in said pressurized continuous flow reactor system so that in the resulting reaction mixture alkyl ester of levulinic acid is formed by a protic acid-catalyzed reaction of furfuryl alcohol with said aliphatic alcohol,
wherein the second supply flux supplies 2.6*10−2 moles to 9*10−1 moles of protic acid per mole of furfuryl alcohol supplied by the first supply flux, in view of the teachings of Parton.
Claims 1-6, 8, 11 and 16-21 are rejected under 35 U.S.C. 103 as being unpatentable over Jing (Jing, F. et al. International publication WO2010/102203A2; cited in IDS06/30/2026).
Regarding claim 1, 11, and 16-18, Jing teaches a process for forming an alkyl ester of levulinic acid or one or more reaction products thereof, said process comprising at least the following steps: (i) preparing or providing a first supply flux comprising furfuryl alcohol and aliphatic alcohol, and a second supply flux comprising at least one protic acid, wherein said protic acid is selected from the group consisting of sulfonic acid optionally selected from the group consisting of an alkyl-aromatic sulfonic acid, an aromatic sulfonic acid, a halosulfonic acid, and an aliphatic sulfonic acid; optionally, the sulfonic acid catalyst is p-toluenesulfonic acid or its monohydrate, 7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonic acid (camphor sulfonic acid) or methanesulfonic acid; or hydrates of each thereof, (ii) supplying the first supply flux and the second supply flux prepared or provided in step (i) to a pressurized continuous flow reactor system and contacting the first supply flux and the second supply flux in said pressurized continuous flow reactor system so that in the resulting reaction mixture alkyl ester of levulinic acid is formed by a protic acid-catalyzed reaction of furfuryl alcohol with said aliphatic alcohol, wherein the second supply flux supplies 1*10-4 to 2.5xl0-2 of protic acid per mole of furfuryl alcohol supplied by the first supply flux.
Regarding claim 2, the aliphatic alcohol of the reference is selected from methanol, n-propanol, isopropanol, n-butanol, and isobutanol (page 5). Jing further teaches the formation of methyl levulinate, n-propyl levulinate, isopropyl levulinate, or n-butyl levulinate (page 5).
Regarding claim 3, Jing teaches that the protic acid includes sulfuric acid,
pyrosulfuric acid, perchloric acid, a phenylsulfonic acid, methanesulfonic acid,
trifluoromethanesulfonic acid, p-toluenesulfonic acid, 1-napthalenesulfonic acid, 2-
napthalene sulfonic acid, chlorosulfonic acid, fluorosulfonic acid, and the like (page 5).
Regarding claims 4 and 19, the reference teaches The optimum yield of alkyl levulinate is realized, and formation of insoluble tarry materials is minimized, when the temperature is maintained for the duration of the reaction at very slightly below, to about 5°C below the temperature where vigorous boiling is observed (page 8). Furthermore, the reference teaches that a crude reacted mixture contains at least about 70 mole percent yield and up to about 90 mole % yield of alkyl levulinate based on furfuryl alcohol (page 10) and the overall conversion of furfuryl alcohol to levulinate species was 90.70 mol% (page 32). Selectivity is calculated by yield/conversion and thus at yield of 70-90%, the selectivity would be about 77%-99.2%.
Regarding claims 5 and 20-21, based on Example 2, the concentration of furfuryl alcohol in the reaction mixture is about 2.97 wt% (based on the total weight of 1656.32 g); and the reaction is carried out at a temperature between about 95-160°C (page 8).
Regarding claim 6, no compound selected from the group consisting of compounds of Bi, Ga, Al, Sn and Fe, is present in the reaction mixture.
Regarding claim 8, non-reacted aliphatic alcohol is separated from the product flux leaving the pressurized continuous flow reactor system, and said non-reacted aliphatic alcohol is recycled to said pressurized continuous flow reactor system wherein alkyl ester of levulinic acid is formed by a protic acid-catalyzed reaction of furfuryl alcohol with said aliphatic alcohol (page 13).
Regarding claim 1, the difference between the claimed invention and Jing is that in the claim, 2.6*10−2 moles to 9*10-1 of protic acid per mole of furfuryl alcohol is supplied whereas in Jing 1*10-4 to 2.5xl0-2 moles of protic acid per mole of furfuryl alcohol is supplied. In view of MPEP § 2144.05, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Thus, absent any showing of criticality or unexpected results, the instantly claimed mole of protic acid per mole of furfuryl alcohol is prima facie obvious over that of Jing.
It would thus have been prima facie obvious to a skilled artisan before the effective filing date of the instant invention to conduct a process for forming an alkyl ester of levulinic acid or one or more reaction products thereof, said process comprising at least the following steps (i) preparing or providing a first supply flux comprising furfuryl alcohol and aliphatic alcohol, and a second supply flux comprising at least one protic acid, wherein said protic acid is selected from the group consisting of sulfuric acid, halogen sulfonic acids, aliphatic sulfonic acids, aromatic sulfonic acids and alkyl-aromatic sulfonic acids, (ii) supplying the first supply flux and the second supply flux prepared or provided in step (i) to a pressurized continuous flow reactor system and contacting the first supply flux and the second supply flux in said pressurized continuous flow reactor system so that in the resulting reaction mixture alkyl ester of levulinic acid is formed by a protic acid-catalyzed reaction of furfuryl alcohol with said aliphatic alcohol,
wherein the second supply flux supplies 2.6*10−2 moles to 9*10−1 moles of protic acid per mole of furfuryl alcohol supplied by the first supply flux, in view of the teachings of Jing.
Claim 7 is rejected under 35 U.S.C. 103 as being unpatentable over Parton (Parton, R. et al. Patent application publication number US2023/0322655A1; effectively filed on Aug. 14, 2020) as applied to claims 1-2, 4-6, 8, 10-11 and 16-21 above, and further in view of Sahib (Sahib, S. “Industrial Chemistry” 2018-2019, pages 1-8).
Claim 7 is rejected under 35 U.S.C. 103 as being unpatentable over Jing (Jing, F. et al. International publication WO2010/102203A2; cited in IDS06/30/2026) as applied to claims 1-6, 8, 11 and 16-21 above, and further in view of Sahib (Sahib, S. “Industrial Chemistry” 2018-2019, pages 1-8).
The teachings of Parton and Jing have been set forth above.
Regarding claim 9, the references fail to teach that the pressurized continuous flow reactor system comprises a material selected from the group consisting of stainless steel and nickel alloys. The deficiency is cured by Stallkamp.
Sahim teaches a continuous stirred tank reactor comprising corrosion resistant material such stainless steel to prevent or minimize corrosion from the use of acids in a chemical reaction. Thus, a skilled artisan would have been motivated in using the CSTR of Sahib in the process of Parton or Jing with a reasonable expectation of success in minimizing corrosion of the reactor by the use of protic acid catalysts.
It would thus have been prima facie obvious to a skilled artisan before the effective filing date of the instant invention to conduct a process for forming an alkyl ester of levulinic acid or one or more reaction products thereof, said process comprising at least the following steps (i) preparing or providing a first supply flux comprising furfuryl alcohol and aliphatic alcohol, and a second supply flux comprising at least one protic acid, wherein said protic acid is selected from the group consisting of sulfuric acid, halogen sulfonic acids, aliphatic sulfonic acids, aromatic sulfonic acids and alkyl-aromatic sulfonic acids, (ii) supplying the first supply flux and the second supply flux prepared or provided in step (i) to a pressurized continuous flow reactor system and contacting the first supply flux and the second supply flux in said pressurized continuous flow reactor system so that in the resulting reaction mixture alkyl ester of levulinic acid is formed by a protic acid-catalyzed reaction of furfuryl alcohol with said aliphatic alcohol,
wherein the second supply flux supplies 2.6*10−2 moles to 9*10−1 moles of protic acid per mole of furfuryl alcohol supplied by the first supply flux, wherein the pressurized continuous flow reactor system comprises a material selected from the group consisting of stainless steel and nickel alloys in view of the combination of Parton and Sahib or of Jing and Sahib.
Claim 9 is rejected under 35 U.S.C. 103 as being unpatentable over Parton (Parton, R. et al. Patent application publication number US2023/0322655A1; effectively filed on Aug. 14, 2020) as applied to claims 1-2, 4-6, 8, 10-11 and 16-21 above, and further in view of Feng (Feng, X. et al. “Fe–Mo2C: A Magnetically Recoverable Catalyst for Hydrogenation of Ethyl Levulinate Into γ‑Valerolactone” Catalysis Letters (2020) 150:2027–2037).
Claim 9 is rejected under 35 U.S.C. 103 as being unpatentable over Jing (Jing, F. et al. International publication WO2010/102203A2; cited in IDS06/30/2026) as applied to claims 1-6, 8, 11 and 16-21 above, and further in view of Feng (Feng, X. et al. “Fe–Mo2C: A Magnetically Recoverable Catalyst for Hydrogenation of Ethyl Levulinate Into γ‑Valerolactone” Catalysis Letters (2020) 150:2027–2037).
The teachings of Parton and Jing have been set forth above.
Regarding claim 9, while the references teach the separation of aliphatic alcohols, the references fail to teach a step of (iii) chemically converting the alkyl ester of levulinic acid formed in step (ii) into one or more reaction products, wherein chemically converting said alkyl ester of levulinic acid into one or more reaction products, wherein said one or more reaction products are selected from the group consisting of levulinic acid, 1,4-pentanediol, gamma-valerolactone, alpha-angelicalactone, beta-angelicalactone and 2-methyl-tetrahydrofuran. The deficiency is cured by Feng.
Feng teaches a catalytic conversion of ethyl levulinate into gamma-valerolactone. The reference further teaches that gamma-valerolactone is an important platform molecule and has the potential application in many areas including clean fuel precursors, green solvents, food additives, value-added synthetic intermediates and flavoring agents. Accordingly, a skilled artisan would have been motivated in using the methods of Feng in the process of Parton or Jing with a reasonable expectation of success in converting ethyl levulinate to the useful gamma-valerolactone product.
It would thus have been prima facie obvious to a skilled artisan before the effective filing date of the instant invention to conduct a process for forming an alkyl ester of levulinic acid or one or more reaction products thereof, said process comprising at least the following steps (i) preparing or providing a first supply flux comprising furfuryl alcohol and aliphatic alcohol, and a second supply flux comprising at least one protic acid, wherein said protic acid is selected from the group consisting of sulfuric acid, halogen sulfonic acids, aliphatic sulfonic acids, aromatic sulfonic acids and alkyl-aromatic sulfonic acids, (ii) supplying the first supply flux and the second supply flux prepared or provided in step (i) to a pressurized continuous flow reactor system and contacting the first supply flux and the second supply flux in said pressurized continuous flow reactor system so that in the resulting reaction mixture alkyl ester of levulinic acid is formed by a protic acid-catalyzed reaction of furfuryl alcohol with said aliphatic alcohol,
wherein the second supply flux supplies 2.6*10−2 moles to 9*10−1 moles of protic acid per mole of furfuryl alcohol supplied by the first supply flux, and further conducting a step of (iii) chemically converting the alkyl ester of levulinic acid formed in step (ii) into one or more reaction products, wherein chemically converting said alkyl ester of levulinic acid into one or more reaction products comprises elimination of aliphatic alcohol, wherein said one or more reaction products are selected from the group consisting of levulinic acid, 1,4-pentanediol, gamma-valerolactone, alpha-angelicalactone, beta-angelicalactone and 2-methyl-tetrahydrofuran
in view of the combination of Parton and Feng or of Jing and Feng.
Conclusion
Claims 1-11 and 16-21 are rejected and no claims are allowed.
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/MEDHANIT W BAHTA/ Primary Examiner, Art Unit 1692
