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 .
DETAILED ACTION
This Office action is responsive to Applicant's preliminary amendment filed Nov. 27, 2023. As filed Claims 1-20 are pending.
Priority
This application filed 11/27/2023 is a National Stage entry of PCT/FR2022/051001 , International Filing Date: 05/27/2022 claims foreign priority to 2105616, filed 05/28/2021.
Information Disclosure Statement
Applicants' information disclosure statements (IDS) have been considered except where lined through. Please refer to Applicants' copy of the 1449 submitted herein.
Claim Objections
Claim 1 is objected to because of the following informalities: the chemical formula drawing should be replaced to show correct bonding (e.g. oxygen appears to be off centered to the double bond.
In claim 1, the recitation “previously” regarding definition of variable R should be omitted to avoid potential indefiniteness issues.
In claims 3 and 17 the recitation “derivative” should be omitted to avoid potential indefiniteness issues.
Appropriate correction is required.
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 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 of this title, 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 set forth in Graham v. John Deere Co., 383 U.S. 1, 148 USPQ 459 (1966), that are applied 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.
1.Claims 1-8, 11 -19 are rejected under 35 U.S.C. 103 as being unpatentable over Fujiwara et al Org. Process Research and Development, 2020, 1988-1995 (cited by Applicants in IDS: supporting information attached herewith) and US 9,789,455 Oct. 17, 2017, by Bedoukian (cited by Applicants in IDS) and further in view of Giani et al. Computers and Chemical Engineering 29 (2005) 1661–1676 (cited in PTO-892 attached herewith).
Instant claims are drawn to method for preparing an aldehyde of general formula (II) wherein the method is continuous and comprises the following concomitant steps:
a) feeding a continuous reactor under an oxygen pressure of between 1 and 30 bar with: i) an alcohol of general formula (I) in solution in an apolar organic liquid phase (A) with a density less than 0.7,
ii) a copper-based catalyst in solution in a polar liquid phase (B) with a density greater than or equal to 0.75,to 0.75; the phases (A) and (B) being immiscible with each other, the alcohol/copper-based catalyst molar ratio ranging from 0.01 to 0.5, from 0.01 to 0.5;
b) recovering the aldehyde in phase (A) by liquid/liquid separation.
The article by Fujiwara teaches continuous -flow aerobic oxidation with a catalytic Cu/TEMPO system and diluted oxygen (5% O2 in N2) to provide a lipid aldehyde 5 (which corresponds to the compound of Formula I of instant claims in which R is linear hydrocarbon n is 17, p is 2 ) by reacting alcohol 4 ( which corresponds to the compound of Formula II of instant claims in which R is linear hydrocarbon n is 17, p is 2 copper containing catalyst -as shown in scheme 3 on page 1989 and Fig 4 page 1992 to give the aldehyde product in 92% yield (instant claims 1 and 3, 12, 15).
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Disclosed on Table 1 page 1990 of the article by Fujiware is the optimization of the reaction conditions for the oxidation of alcohol 4 to aldehyde 5, increasing the oxygen feed rate, back pressure, and reaction temperature ( entries 2-9). Final optimization at 0.40 mL/min was started with an oxygen feed rate of 50 mL/
min, a back pressure of 8 bar, and a reaction temperature of 80°C (instant claim 1; 12, 15).
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Regarding instant claims 2-5, 14, 11,16, 17, the example on page 1994 of the article by Fujiware teaches NMI, N-Methylimidazole, TEMPO, 2,2,6,6-tetramethylpiperidin-l-oxyl; NMP, N-methylpyrrolidone (solvent); bipyridine, and the reaction carried in a SUS tube reactor:
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Regarding the polar organic liquid of instant claim 7, disclosed on Table S2 and Table S3 in the supporting information of Fujiware is the solvent investigation including acetonitrile as solvent for the reaction.
Regarding instant claims 2 and limitation of claim 15 of the preparing, in a mixer M, a homogeneous two-phase mixture comprising the alcohol the prior art teaches on Table S4 Ligand screening and homogeneous reaction state:
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The method of the present application differs from the method described in the article by Fujiwara in that prior art does teach the reaction in liquid phases immiscible and does not teach step b of claimed process liquid/liquid separation for the formation of the same compound; the Fujiwara does not specify concomitant feeding reactants to the reactor.
Regarding the limitation of specify concomitant feeding reactants to the reactor, the prior art by ‘455 patent teaches an exceptional mixing on a relatively small scale and desirable removal of product from the reaction medium applicable to oxidation reactions; wherein synthesizing compounds can include providing at least two chemical components in a vortical layer. Vortical movement of the at least two chemical components is generated at least two chemical components is converted to at least one reaction; the synthesized compounds and/or reaction products and/or product mixtures can be removed from the vessel; Depending on the particular components in the outlet
stream, separations can include a gas-liquid separator or liquid-liquid separation process; (col 3 lines 45-67, continuing to col 4 line 1-65). The advantages of the method by the ‘455 patent include simplicity of the method and reactor apparatus, superior ability to handle solids without clogging, excellent heat transfer,
and low cost of the method and reactor apparatus (col 2 lines 42-49).
Therefore, the prior art relied upon, and knowledge generally available in the art before the effective filing date provide some suggestion that would have motivated the skilled artisan to conduct the process for oxidation of alcohol to aldehyde taught by Fujiwara in a concominted methodology as disclosed by the ‘455 patent to increase the efficiency of the process.
Regarding the limitation of instant claims about the apolar solvent in liquid phase A and polar solvent in liquid phase B, the phases (A) and (B) being immiscible with each and separation by liquid/liquid extraction, choosing an appropriate solvent for the reaction and separation of the product by extraction, are routine in chemical art and are the known options within the technical grasp of one of ordinary skill in the art.
As discussed in the article by Gani selection of appropriate solvents for the promotion of organic reactions, by using a rules-based procedure where the estimated reaction-solvent properties and the solvent properties guide the decision making process is known in the art. Example 4 on page 1673-1674 showed that for oxidation reaction, the solvent needs to dissolve the alcohol substrate, must be inert and must be liquid at the reacting condition, it must have favorable EHS properties and must have a density close to that of water; based on the criteria, a list of candidate solvents are generated through ProCamd program, providing a breakdown of number of feasible chemicals that have been found to satisfy the specified solvent property constraints. Gani teaches extraction as separation methodology (pages 1673-1674).
Based on the teaching of prior art combined with technical knowledge, a person having ordinary skill in the art would opt for appropriate solvent as reaction solvent and solvent for extraction, with reasonable expectation of success.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention, to combine the teachings of the cited prior art and to produce aldehyde by oxidation of alcohol mediated by a copper- based catalyst by the method taught by Fujiwara under suitable reaction solvent, in a concominted methodology followed by liquid/liquid extraction as disclosed by the ‘455 patent and to screen the appropriate solvent for the reaction, to arrive at instant invention with reasonable expectation of success, because the prior art teach that optimizing the reaction conditions by selection of solvent is routine in the chemical art.
In conclusion, the prior art as a whole, teaches the elements of the claimed method for producing aldehydes by oxidation of alcohols mediated by copper-based catalyst (a) and (b) with a reasonable expectation of success, that the invention would be prima facie obvious to one of ordinary skill.
"Exemplary rationales that may support a conclusion of obviousness include: (A) Combining prior art elements according to known methods to yield predictable results ". See MPEP § 2143.
Therefore, absent a showing of unexpected results, the instant claims are obvious over the prior art.
2.Claims 1-20 are rejected under 35 U.S.C. 103 as being unpatentable over Fujiwara et al Org. Process Research and Development, 2020, 1988-1995 (cited by Applicants in IDS; supporting information attached herewith), US 9,789,455 Oct. 17, 2017, by Bedoukian (cited by Applicants in IDS) and Giani et al. Computers and Chemical Engineering 29 (2005) 1661–1676 (cited in PTO-892 attached herewith) as applied to claims 1-8, 11 -19 above and further in view of Vanoye et al. Adv. Synth. Catal. 2015, 357, 739-746 (cited by Applicants in IDS).
The combined teachings of Fujiwara, the ‘455 patent and Giani pertaining to claims 1-8, 11 -19 are outlined above.
The cited prior art teaches Cu(I) as copper-based catalyst for oxidation of alcohol to aldehyde, it does not teach Cu (II) as required by claims 9-10, 20.
However, it is noted that oxidation of alcohol to aldehyde mediated by Cu(II) as alternative catalyst is discussed in the article by Vanoye.
Regarding the oxidation under , the article by Vanoye teaches aerobic oxidation using a combination of copper salts and 2,2,6,6-tetramethylpiperidine Noxyl
(TEMPO) for organic synthesis; these catalytic systems were evaluated in a gasliquid
segmented flow device. The improvement of oxygen mass transfer has a significant influence on the turnover-limiting step. As such, an improved catalytic system using copper(II) as copper source in acetonitrile was implemented in a microreactor for the safe and efficient oxidation of primary alcohol (abstract). Disclosed on table 1 page 742 and table 2 page 743 of the article by Vanoye are examples of Cu(II) catalyst including Cu(II) Br2 ( instant claim 9, 10, 20). Disclosed on page 744 of Vanoye is that the direct aerobic oxidation of primary alcohols to the corresponding
aldehydes can be dramatically enhanced by using continuous-flow methodology with a Cu/TEMPO catalytic system and pressurised molecular oxygen at room temperature; the speciation of the Cu species in solution has a significant effect of the kinetics profile of the Cu/TEMPO catalytic system. Stabilization of Cu(II)OH using excess of bpy and NMI is essential for the catalytic activity. Cu(II) salts could be used instead of Cu(I)
and the reaction times could be significantly reduced from hours to minutes.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention, to combine the teachings of Fujiwara concerning oxidation reaction of alcohol to aldehyde with copper-based catalyst with the teachings of Vanoye and use Cu(II) mediated oxidation instead of Cu(I), and have reasonable expectation of success in arriving at the claimed invention, because the prior art teach that Cu(II) salts could be used instead of Cu(I) and the reaction times could be significantly reduced.
The rationale to support a conclusion that the claim would have been obvious is that teaching, suggestion, or motivation in the prior art that would have led one of ordinary skill to modify the prior art reference or to combine prior art reference teachings to arrive at the claimed invention. KSR, 550 U.S. at_, 82 USPQ2d at 1395.
Thus, the claimed invention as a whole is prima facie obvious over the combined teachings of the prior art.
Conclusion
Claims 1-20 are rejected.
Telephone Inquiry
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ANA MURESAN whose telephone number is (571)-270-7587. The examiner can normally be reached on Monday through Friday, 8:30 am to 5:30 pm EST.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Scarlett 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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/ANA Z MURESAN/Primary Examiner, Art Unit 1692
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