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
Claims 1-20 of S. Groessl et al., US 18/846,324 (Mar. 30, 2023) are pending. Claims 13-16, to non-elected inventions of Groups (II)-(IV) are withdrawn from consideration pursuant to 37 CFR 1.142(b). Claims 1-12 and 17-20 are under examination on the merits and are rejected.
Election/Restrictions
Applicant elected the claims of Group I (i.e., claims 1-12 and 17-20), drawn to a process for producing a tertiary amine surfactant, with traverse in the Reply to Restriction Requirement filed on July 21, 2026. Claims 13-16, to non-elected inventions of Groups (II)-(IV) are withdrawn from consideration pursuant to 37 CFR 1.142(b)The restriction/election requirement is made FINAL.
Applicant’s Traversal
Applicant traverses on the ground that all the groups of claims are connected at least by the tertiary amine surfactant. Reply at page 7. Applicant argues that no additional search burden would be present during examination; any art relevant to the process for producing a tertiary amine surfactant of general formula (I) (Group I claims) would be relevant to the surfactant composition, comprising a surfactant of general formula (I) or a salt thereof (Group II claims), the select compounds that fall within the scope of general formula (I) (Group III claims), and the method of using the compound according to claim 15, the method comprising using the compound as a surfactant (Group IV claims).
This argument is not considered persuasive because the instant restriction was issued under the unity-of-invention rules governing restriction in international applications under 35 U.S.C. 371 (see MPEP § 802; MPEP § 1893.03(d); 37 CFR § 1.499), therefore the search burden requirement set forth in MPEP 803 does not apply in the instant case. Under the applicable PCT rules there is no requirement of a serious search burden. The instant Application is an international application entering the National Stage under 35 U.S.C. 371. Under the rules governing multiple inventions under 35 U.S.C. 371 (see MPEP § 1893.03(d)), an international application should relate to only one invention or, if there is more than one invention, the inclusion of those inventions in one international application is only permitted if all inventions are so linked as to form a single general inventive concept (Rule 13.1). International Preliminary Examination Under Chapter II Of The PCT, Chapter 10, Unity of Invention, (Oct. 3, 2011). As such, in the instant case, there is no requirement that the Examiner prove or show a serious search burden.
Claim Rejections - 35 USC § 103
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 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 AIA 35 U.S.C. 103(a) 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.
Claims 1-3, 5, 7-11, 17 and 20 are rejected under AIA 35 U.S.C. 103 as being unpatentable over S. Clendennen et al., US 2019/0218170 (2019) (“Clendennen”).
Claim 4 is obvious over Clendennen as above, in further view of N. Do et al., US 2024/0208894 (2024) (“Do”) and/or J. Eberhardt et al., US 2010/0267948 (2010) (“Eberhardt”) and/or S. Forsyth et al., 10 Organic Process Research & Development, 94-102 (2006) (“Forsyth”)
Claim 6 is rejected over Clendennen as above, in further view of N. Do et al., US 2024/0208894 (2024) (“Do”) and/or J. Eberhardt et al., US 2010/0267948 (2010) (“Eberhardt”) and/or S. Forsyth et al., 10 Organic Process Research & Development, 94-102 (2006) (“Forsyth”).
Claim 12 is obvious over Clendennen as above, in further view of J Kao et al., US 5,625,098 (1997) (“Kao”).
Claim 18 is obvious over Clendennen as above, in further view of D. Nageshwar et al., 20 Synthetic Communications, 3357-3368 (2009) (“Nageshwar”), Do and/or Eberhardt
Claim 19 is obvious over Clendennen, Nageshwar, Eberhardt and/or Do as above for claim 18 in further view of J. Jiang et al., CN 105481744 (2016) (“Jiang”).
S. Clendennen et al., US 2019/0218170 (2019) (“Clendennen”)
Clendennen teaches trialkylamines of the following formula:
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wherein R1 and R2 are each independently selected from straight or branched chain or cyclic hydrocarbon radicals having 1 to 8 carbon atoms; wherein R5, R6 and R7 are independently at least one of C3H7, C2H5, CH3, or H, or combinations thereof; and wherein R5 and R6 are not H at the same time. Clendennen at page 1, [0011].
Clendennen further teaches N-alkyl-N-methylglucamines having the formula
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wherein R5, R6 and R7 are C3H7, C2H5, CH3, or H, and Z is a polyhydroxyhydrocarbyl moiety derived from a reducing sugar in a reductive amination reaction. Clendennen at page 4, [0070].
Clendennen teaches that the disclosed amines are useful in the field of surfactants. Clendennen at page 10, [0199]. Clendennen teaches that C10 to C12 aldehydes are reacted with a secondary amine under reductive conditions to produce trialkylamines. Clendennen at page 15, [0259].
With respect to the reductive amination, Clendennen teaches:
[0261] The reductive amination of ketones or aldehydes towards trialkylamines can be done in either one or two process steps in which the first step comprises the reaction of the ketone or aldehyde with an amination reagent such as dimethylamine to form an intermediary imine or enamine followed by the second process step in which the intermediary imine or enamine is hydrogenated towards the desired amine. The reductive amination reaction of ketones or aldehydes can be done in a gas- or liquid-phase process in the presence of a reducing agent, an amine and if deemed necessary, a suitable catalyst. The reductive amination reaction can be performed in a reaction medium comprising a solvent.
[0264] This reaction can be performed either batch wise or continuous. If a continuous installation is used, this can be either a continuous stirred tank reactor (CSTR) or plug flow reactor. The temperature can range from 80 to 300° C and the pressure from 1 bara to 100 bara. As used herein, "bara" means (Absolute Pressure) Pressure reading relative to absolute vacuum.
Clendennen at page 15, 16, [0261], [0264].
With respect to the reductive-amination catalyst, Clendennen teaches Raney nickel, palladium, rhodium, ruthenium, platinum, or combinations thereof. Clendennen at page 5, [0099]. Nickel, palladium and platinum are, per claim 1, “heterogeneous catalyst comprising a group 10 element”. Clendennen teaches that the catalyst may be carried upon a heterogeneous support for ease of removal from the reaction medium and supports can include carbon, alumina, silica, or mixtures thereof, and the like. Clendennen at page 5, [0100].
Clendennen teaches the reaction between N-monoalkylglucamine and aldehydes can be carried out at a temperature from 50 and 170° C, or from 75 and 145° C, or from 100 and 120° C. Clendennen at page 5, [0106]; Id. at page 15, [0255].
Clendennen teaches working Example 37, which is summarized by the Examiner as follows:
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Clendennen at page 25, [0372]. Clendennen Example 37 meets each and every chemical-structure limitation of claim 1, where decanal meets the limitations of claim 1 formula (II); N-methylglucamine meets the limitations of claim 1, formula (III), and the product, N-decyl-N-methylglucamine meets the limitations of claim 1, formula (I). Clendennen Example 37 differs from claim 1 in that the reaction temperature is not disclosed (claim 1 requires “temperature in the range of 25 to 70 °C”) and Example 37 is performed at a hydrogen pressure of 60 bar (claim 1 requires “at least 1 bara to less than 40 bara”).
Clendennen teaches working Example 50, which is summarized by the Examiner as follows:
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Clendennen at page 27, [0379]. Clendennen Example 50 meets each and every chemical-structure limitation of claim 1 and differs from claim 1 only in that the reaction was performed at “room temperature”1 (claim 1 requires “temperature in the range of 25 to 70 °C”).
Clendennen Meets the Claim 1 Limitation of “feed operation”
At least Clendennen Example 50 meets the claim 1 limitation of “feed operation”.
Claim 1 . . . wherein the reductive amination is conducted in feed operation . . .
as this term is broadly and reasonably interpreted, consistently with the specification. The term “feed operation” does not appear to be an art-recognized term having a particular meaning. As such, “feed operation” is given its plain meaning, consistent with the specification. MPEP § 2111. With respect to the meaning of “feed operation” the specification teaches the following relevant portion:
The process of the invention is conducted in feed operation, wherein the secondary amine of general formula (Ill) is provided (i.e., initially charged), and the aldehyde of general formula (II) is metered thereto.
Specification at page 8, lines 34-36. The specification body gives no additional guidance, for example, what the purpose/benefit is of a “feed operation”. Specification working examples 1 and 9 simply mix the aldehyde (II), amine (III) and catalyst (Pd/C) under hydrogen pressure at a specified temperature, to give tertiary amine (I). Specification at pages 19, 21. Specification Examples, 1 and 9 clearly do not employ the claimed “feed operation”. On the other hand, specification Examples 2-8 teach first mixing amine (III) and catalyst (Pd/C) and applying an initial hydrogen pressure, warming the mixture to the reaction temperature, and then metering in the aldehyde (II) over a period of time. Specification at pages 19-20. From the data in Table 1 (pages 21-22), the Examiner finds that no criticality with respect to the addition procedure of Examples 1 and 9 versus that of Examples 2-8 is immediately apparent.
In view of the foregoing, the claim 1 term “wherein the reductive amination is conducted in feed operation” is broadly and reasonably interpreted, consistently with the specification as meaning that that the process of claim 1 is conducted by adding the aldehyde (II) to the amine (III), where amine (III) is already present in a reaction vessel. MPEP § 2111.
Clendennen working Example 50 meets the claim 1 limitation of “wherein the reductive amination is conducted in feed operation” because Clendennen teaches that C11-aldehyde is added to a mixture the Raney Ni catalyst, dimethylamine, and ethanol. Clendennen at page 27, [0380]. It is not clear whether Clendennen Example 37 meets this limitation, because the order of reagent addition is not specified.
Differences between Clendennen and Claim 1
Clendennen teaches each and every limitation of claim 1, but does not put these teachings together in in a single embodiment.
Clendennen Example 37 meets each and every chemical-structure limitation of claim 1, where decanal meets the limitations of claim 1 formula (II); N-methylglucamine meets the limitations of claim 1, formula (III), and the product, N-decyl-N-methylglucamine meets the limitations of claim 1, formula (I). Clendennen Example 37 differs from claim 1 in that the reaction temperature is not disclosed (claim 1 requires “temperature in the range of 25 to 70 °C”) and Example 37 is performed at a hydrogen pressure of 60 bar (claim 1 requires “at least 1 bara to less than 40 bara”).
Clendennen Example 50 meets each and every chemical-structure limitation of claim 1, where Clendennen’s hydrogen pressure (30 psa or 2 bar) falls within the claimed range of “at least 1 bara to less than 40 bara”. Clendennen Example 50 differs from claim 1 only in that the reaction was performed at “room temperature” (i.e., a temperature in the range of 20 °C to about 25 °C, see footnote 1), where claim 1 requires “temperature in the range of 25 to 70 °C”.
N. Do et al., US 2024/0208894 (2024) (“Do”)
Prior Art Effect of Do
The earliest possible effective filing date of the subject claims is that of priority document EP 22165296.9 (Mar. 30, 2022). Do is effective prior art under 35 USC § 102(a)(2) respecting the subject matter cited in this rejection as of the filing date of Do’s priority document 63/324,162 (Mar. 28, 2022) because: (1) Do is U.S. patent application publication; (2) names another inventor; and (3) the subject matter of Do relied upon in this rejection is disclosed in Do’s priority document 63/324,162 (Mar. 28, 2022). See MPEP § 2154.01; 35 USC § 102(d). Thus, the effective filing date of the subject matter relied upon in this rejection is Mar. 28, 2022, which is before the claims’ earlies possible effective filing date of March 30, 2022. See MPEP § 2154.01; 35 USC § 102(d).
Relied-Upon Teachings of N Do et al., US 2024/0208894 (2024) (“Do”)
In view of the above prior art discussion, citations are made to Do’s priority document 63/324,162 (Mar. 28, 2022). Do teaches a method for producing a compound having a chemical formula of Formula I. 63/324,162 at page 3, [0008]. Do teaches that the compounds of Formula I can be prepared by reductive amination. 63/324,162 at page 66, [0338].
Do teaches that the reduction of the ester aldehyde(s) with the amine and hydrogen can be catalyzed with a metal catalyst. In some aspects, the metal catalyst contains a platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), and/or iridium (Ir) catalyst. 63/324,162 at page 68, [0345].
In working Example 6, Do teaches the following reductive amination of aldehyde (C-3) and 4-amino-1-butanol with hydrogen (H2) over platinum-carbon(Pt-C) catalyst to form a cationic lipid (C-4), according to the Scheme E4.
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63/324,162 at page 87, [0378]. Do’s catalyst Pt/C meets the claim 1 limitation of “heterogeneous catalyst comprising a group 10 element of the periodic table of the elements”. Do’s hydrogen pressure of 75 psi (5 bar) and temperature of 35 °C falls within the claim 1 temperature and pressure ranges.
Claim 1 . . . wherein the reductive amination is performed at
a pressure of molecular hydrogen in the range of at least 1 bara to less than 40 bara; and
at a temperature in the range of 25 to 70 °C.
However, Do’s reactants and products differ from those of claim 1 because Do’s corresponding R1 is substituted with a hydroxyl group (which is not permitted by claim 1) and Do’s corresponding R2 and R3 are substituted by ester groups (which is also not permitted by claim 1).
J. Eberhardt et al., US 2010/0267948 (2010) (“Eberhardt”)
Eberhardt teaches a process for preparing an amine by reacting an aldehyde and/or ketone with hydrogen and a nitrogen compound selected from the group consisting of primary and secondary amines in the presence of a heterogeneous catalyst. Eberhardt at page 1, [0001]. Eberhardt teaches that the process of the invention enables aldehydes and ketones to be converted into the corresponding secondary and tertiary amines with high selectivity and in high yield. Eberhardt at page 3, [0038].
With respect to aldehyde addition and temperature, Eberhardt teaches:
[0020] In a particularly preferred embodiment of the invention, the addition rate of the aldehyde and/or the ketone is selected so that the respective desired maximum temperature (preferably in the range from 70 to 180°C.) of the reaction is not exceeded. (Rate of addition in, for example, mol of aldehyde and/or ketone per 30 minutes).
Eberhardt at page 2, [0020]. Thus, Eberhardt teaches metered addition of aldehyde to a mixture of amine and catalyst to avoid a reaction exotherm.
Eberhardt teaches that a catalyst which is particularly preferred for the purposes of the present invention is Pd on activated carbon (Pd/C). Eberhardt at page 3, [0032].
Eberhardt teaches a working-example series where 33 runs (at specific temperatures/pressures) of the reductive amination of 2-ethylhexanal and bis(2-ethylhexylamine), mediated by Pd/C, to produce tris(2-ethylhexylamine), were conducted. Eberhardt at pages 7-8, [0111] (data in Table 3). The reductive amination was conducted in a stirring autoclave first adding the bis(2-ethylhexylamine) and Pd/C catalyst and as soon as the reaction temperature had been reached, the hydrogen pressure was increased to the desired reaction pressure and the 2-ethylhexanal was subsequently added continuously. Eberhardt at page 7, [0111].
The reaction is summarized by the Examiner below.
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Eberhardt at page 7, [0111].
It is noted that the only difference between the above cited working example and instant claim 1 is the temperature/pressure at which Eberhardt’s above working-example, reductive amination is conducted. That is Eberhardt’s 2-ethylhexanal meets the limitations of claim 1 formula (II); bis(2-ethylhexylamine) meets the limitations of claim 1, formula (III), and the product, tris(2-ethylhexylamine) meets the limitations of claim 1, formula (I).
D. Nageshwar et al., 20 Synthetic Communications, 3357-3368 (2009) (“Nageshwar”)
Nageshwar teaches the following room-temperature (see footnote 1) reductive amination between 3,7-dimethyl-6-octenal and dimethyl amine under a hydrogen atmosphere, employing Raney nickel as the catalysts.
Preparation of (3S or 3R)-3,7-Dimethyl-6-octenyl (Dimethyl) Amine (3)
To a stirred solution of (3S)- or (3R)-3,7-dimethyl-6-octenal (5.0 g, 32.4 mmol) in methanol (50 mL), 40% aqueous solution of dimethylamine (2.4 mL, 48.6 mmol) and Raney nickel (30% w=v) were added at room temperature. The reaction was left to stir for 20 h at room temperature under a hydrogen environment. After the completion of the reaction, the catalyst was filtered, and the solvent was evaporated under reduced pressure. The resulting crude (pale greenish liquid) was subjected to column chromatography using a mixture of ethyl acetate and pet. ether as an eluent to yield 4.2 g (70%) of pure desired product, (3S)- or (3R)-3, 7-dimethyl-6-octenyl (dimethyl) amine (3).
Nageshwar at page 3362 (emphasis added). Nageshwar’s above reaction is summarized as follows:
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Nageshwar teaches hydrogen pressure by way of a hydrogen balloon. Nageshwar at page 3359 (text of Scheme 1). One of ordinary skill would understand that the hydrogen pressure from a hydrogen balloon would be at about atmospheric (i.e., 1 bar) pressure. See University of Pittsburgh Safety Manual, Hydrogenation Reactions, (2019) (“2.1 Level 1 – H2 Rx conducted under atmospheric pressure via a reaction balloon filled with hydrogen gas and the reaction vessel is a glass vial, flask or bottle; H2 Rx conducted with a H-Cube ® Continuous-flow Hydrogenation Reactor” (emphases added)).
S. Forsyth et al., 10 Organic Process Research & Development, 94-102 (2006) (“Forsyth”)
As part of study regarding the one-pot synthesis of the fungicide fenpropimorph, Forsyth teaches that Table 1 summarizes the reductive amination of different aldehydes by different bases using 10% Pd/C, 5% Pd/Al2O3, and PdCl2 in the Baskerville miniautoclave. Forsyth at page 96, col. 1 (under heading “Reductive Amination”). Referencing Forsyth Scheme 1 (at page 96), the Examiner summarizes Table 1, Entry 3 as follows:
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See Forsyth at page 97, Table 1, Entry 3. Forsyth thus teaches reductive amination of an aldehyde (not falling within the scope of claim 1 formula (II)) and claimed cyclic amine, using Pd/C, within the instant claim 1 temperature and hydrogen pressure ranges.
Obviousness Rationale
Claim 1 is obvious because one of ordinary skill is motivated to conduct either of Clendennen working Examples 37 or 50 within the claim 1 temperature and pressure ranges:
Claim 1 . . . wherein the reductive amination is performed at
a pressure of molecular hydrogen in the range of at least 1 bara to less than 40 bara; and
at a temperature in the range of 25 to 70 °C.
One of ordinary skill thereby arrives at each and every limitation of claim 1. The claim 1 limitation of “feed operation”.
Claim 1 . . . wherein the reductive amination is conducted in feed operation . . .
does not distinguish over the cited art. As discussed above, the claim 1 term “wherein the reductive amination is conducted in feed operation” is broadly and reasonably interpreted, consistently with the specification as meaning that that the process of claim 1 is conducted by adding the aldehyde (II) to the amine (III), where amine (III) is already present in a reaction vessel. MPEP § 2111. Clendennen working Example 50 meets the claim 1 limitation of “wherein the reductive amination is conducted in feed operation” because Clendennen teaches that C11-aldehyde is added to a mixture the Raney Ni catalyst, dimethylamine, and ethanol. Clendennen at page 27, [0380]. Furthermore, absent a showing of criticality/unexpected results, the order of reagent addition cannot distinguish claim 1 from Clendennen working Example 37. MPEP § 2144.04 (IV)(C).2
It is also important to note that Clendennen working Example 50 only differs from claim 1 in that it is performed at “room temperature” (i.e., a temperature in the range of 20 °C to about 25 °C, see footnote 1), where the claim 1 lower-range-end is 25 °C. Thus, claim 1 is obvious over Clendennen working Example 50 alone because the claimed and reference temperatures are close. A prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. MPEP § 2144.05(I).
Alternatively, claim 1 is obvious because one of ordinary skill is motivated to practice either of Clendennen Examples 37 or 50 within the instantly claimed temperature/pressure ranges because Clendennen teaches overlapping temperature and hydrogen pressure ranges. That is, Clendennen teaches generally that the reductive amination temperature ranges of 50 and 170° C, or from 75 and 145° C, or from 100 and 120° C. Clendennen at page 5, [0106]; Id. at page 15, [0255]. Clendennen also teaches reductive amination temperature/pressure ranges -- a temperature can range from 80 to 300° C and the pressure from 1 bara to 100 bara. Clendennen at page 16, [0264]. In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. MPEP § 2144.05(I). Furthermore, generally, differences in concentration (in this case hydrogen pressure) or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. MPEP § 2144.05(II)(A) (citing In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
One of ordinary skill has a reasonable expectation of success in practicing Clendennen within the claim 1 temperature and pressure ranges because Clendennen working Example 50 is performed at room temperature with a hydrogen pressure (30 psa or 2 bar), which pressure falls within the claimed range of “at least 1 bara to less than 40 bara”. For example, one of ordinary skill is motivated by Clendennen Example 50, to optimize Clendennen Example 37 to temperatures/pressures within the claim 1 ranges. MPEP § 2144.05(II)(A).
Claim 2 is obvious because corresponding variable R1 in both of Clendennen working Examples 37 and 50 is C7-C17-alkyl.
Claim 3 is obvious because corresponding variables R2 and R3 Clendennen working Example 50 is methyl.
Claim 4 is obvious over Clendennen, Nageshwar, Eberhardt and/or Do in further view of L. Hunt et al., US 4,374,850 (1983) (“Hunt”). Hunt teaches that 1-dodedecylpyrrolidine (which meets the chemical structure variables of claim 4 wherein R2 and R3, together with the nitrogen atom to which they are bound, form a pyrrolidinyl group):
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is useful in reducing the number of progeny produced by the ticks. See Hunt at Col. 6, Table 1 (compound 25). Hunt teaches synthesis by lithium aluminum hydride reduction. Hunt at col. 4, lines 7-19. Claim 4 is obvious because one of ordinary skill is motivated to prepare 1-dodedecylpyrrolidine be reductive amination between the corresponding C12 aldehyde and pyrrolidine according to the procedure of any of Clendennen (Example 5), Nageshwar, Eberhardt and/or Do, within the instantly claimed temperature/pressure ranges. One of ordinary skill has a reasonable expectation of success, for example, in using Pd on activated carbon, because Forsyth teaches a similar reductive amination of an aldehyde (not falling within the scope of claim 1 formula (II)) and a claimed cyclic amine, using Pd/C, within the instant claim 1 temperature and hydrogen pressure ranges.
The limitations of claim 5 are clearly met by Clendennen alone because both of Clendennen working Examples 37 and 50 employ the claim 5 alternative of nickel. Alternatively, claim 5 is obvious over Clendennen in view of N Do et al., US 2024/0208894 (2024) (“Do”) for the following reasons. Do’s catalyst Pt/C meets the claim 5 limitation of “platinum”. Do’s hydrogen pressure of 75 psi (5 bar) and temperature of 35 °C falls within the claim 1 temperature and pressure ranges. In working Example 6, Do teaches the reductive amination of aldehyde (C-3) and 4-amino-1-butanol with hydrogen (H2) over platinum-carbon (Pt-C) catalyst to form a cationic lipid (C-4), according to the Scheme E4. 63/324,162 at page 87, [0378]. Do’s hydrogenation is a similar hydrogenation to that of Clendennen working Examples 37 and 50. Further, Clendennen and Do each teach that nickel, platinum and palladium are suitable, alternative reductive-amination hydrogenation catalysts. Clendennen at page 5, [0099] (Ni, Pt, or Pd); Do-63/324,162 at page 68, [0345] (Pd or Pt). As such, one of ordinary skill is motivated to perform either of Clendennen working Examples 37 or 50, with Pt/C as taught by Do, under the temperature and hydrogen pressure ranges of Do (which fall within the range of instant claim 1). One of ordinary skill thereby meets each and every limitation of claim 5.
Claim 6 is obvious over Clendennen in view of Do (under the rationale of claim 5 above) in further view of J. Eberhardt et al., US 2010/0267948 (2010) (“Eberhardt”) and/or S. Forsyth et al., 10 Organic Process Research & Development, 94-102 (2006) (“Forsyth”). Per the above rationale for claim 5, one of ordinary skill is motivated to perform Clendennen working Examples 37 or 50, under the temperature and hydrogen pressure ranges of instant claim 1, with any of nickel, platinum or palladium, because both Clendennen and Do teach these as suitable, alternative reductive-amination hydrogenation catalysts. Clendennen further teaches and that catalyst may be carried upon a heterogeneous support for ease of removal from the reaction medium and supports can include carbon, alumina, silica, or mixtures thereof, and the like. Clendennen at page 5, [0100]. Furthermore, Eberhardt teaches that a reductive amination catalyst which is particularly preferred is Pd on activated carbon (Pd/C). Eberhardt at page 3, [0032]. Eberhardt is directed to the same reductive amination instantly claimed. In view of the foregoing, one of ordinary skill is motivated to replace nickel with palladium on activated carbon as the catalyst for either of Clendennen working Examples 37 and 50, at the claim 1 temperature and hydrogen pressure ranges, thereby arriving at each and every limitation of claim 6. One of ordinary skill has a reasonable expectation of success in using Pd on activated carbon because Forsyth teaches a similar reductive amination of an aldehyde (not falling within the scope of claim 1 formula (II)) and claimed cyclic amine, using Pd/C, within the instant claim 1 temperature and hydrogen pressure ranges.
Claim 7-9 are obvious because Clendennen teaches that the disclosed reductive amination can be performed in the presence of a solvent. Clendennen at page 15, [0261]. Clendennen working Examples 37 and 50 respectively employ methanol and ethanol as solvents.
Claim 10 is obvious for the following reasons. In working Example 37, Clendennen teaches 8.1 g of decanal and 10.1 g N-methylglucamine (total weight 0.0182 kg) and 15 g of methanol (volume is 0.01896 liters) to give a solvent dilution ratio of 1.04 L per kg, which meets the limitations of claim 10.
Claim 11 is obvious because in working Example 50, Clendennen teaches that in isolation of the product tertiary amine “[t]he residue was diluted with EtOAc (200 mL) and 10% aq. HCl (200 mL)”. Clendennen at page 27, [0380]. This meets the claim 11 language “comprising neutralizing the tertiary amine surfactant of general formula (I) with an acid.”
Claim 12 is obvious over Clendennen in further view of J Kao et al., US 5,625,098 (1997) (“Kao”) for the following reasons. Claim 12 recites “bio-based” in the following context.
12. The process according to claim 1, wherein the aldehyde of general formula (II) and/or the secondary amine of general formula (III) are bio-based compounds.
The term “bio-based compound” is broadly and reasonably interpreted, consistently with the specification, as having a greater-than-zero percent of 14C radio isotope. Specification at page 19, lines 18-34 (citing ASTM-D6866 and WO 2007/095262 A2).3
Kao teaches that N-methylglucamine can be prepared by reaction of corn syrup (a bio-based material) with methylamine. Kao at col. 14, lines 35-60 (Example II). The so prepared N-methylglucamine is, per claim 12, a secondary amine of general formula (III) that is bio-based, since it is prepared from corn syrup and will have percent 14C. See footnote 3. Claim 12 is obvious because one of ordinary skill is motivated to perform Clendennen working Example 37 by using N-methylglucamine as prepared by Kao simply as a convenient source of this material. In this regard, Kao teaches that use of these materials in the manner disclosed herein provides superior reaction products. Kao at lines bridging cols. 6-7.
Claim 17 is obvious in view of Clendennen because corresponding variable R1 in Clendennen working Example 37 is a C9 alkyl.
Respecting claim 18, in working Example 40, Clendennen teaches the following reaction:
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Clendennen at page 25, [0373] (third entry in Table 7). Clendennen Example 40 meets each and every organic chemical-structure limitation of claim 18, where 2-ethyl-4-methylhept-2-enal, meets the limitations of claim 1 formula (II), and per claim 18, R1 is C9-alkeneyl; N-methylglucamine (NMG) meets the limitations of claim 1, formula (III), and the product, meets the limitations of claim 1, formula (I). Clendennen Example 40 differs from claim 18 in that Ru is not a claimed metal catalyst, the reaction temperature is 100 °C (claim 1 requires “temperature in the range of 25 to 70 °C”) and Example 40 is performed at a hydrogen pressure of 60 bar (claim 1 requires “at least 1 bara to less than 40 bara”).
Claim 18 is obvious over Clendennen in view of Nageshwar, Eberhardt and/or Do because one of ordinary skill is motivated to practice Clendennen Example 40 with any of Raney Ni, Pd, or Pt instead of Ru, within the instantly claimed temperature/pressure ranges because Clendennen teaches overlapping temperature and hydrogen pressure ranges. That is, Clendennen teaches generally that the reductive amination temperature ranges of 50 and 170° C, or from 75 and 145° C, or from 100 and 120° C. Clendennen at page 5, [0106]; Id. at page 15, [0255]. Clendennen also teaches reductive amination temperature/pressure ranges -- a temperature can range from 80 to 300° C and the pressure from 1 bara to 100 bara. Clendennen at page 16, [0264]. In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. MPEP § 2144.05(I). Furthermore, generally, differences in concentration (in this case hydrogen pressure) or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. MPEP § 2144.05(II)(A) (citing In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955). One of ordinary skill has a reasonable expectation of success in using Raney Ni as the catalyst, in view of Nageshwar because Nageshwar teaches a similar reductive amination with an unsaturated, C8-alkenyl aldehyde at room-temperature (see footnote 1) and dimethyl amine under a hydrogen atmosphere (about 1 bara), employing Raney nickel as the catalysts. One of ordinary skill has a reasonable expectation of success with Pt/C as the catalyst, in view of Do for the same reasons discussed above for claim 5. One of ordinary skill has a reasonable expectation of success with Pd/C as the catalyst, in view of Eberhardt, for the same reasons discussed above for claim 6.
Claim 19 is obvious over Clendennen, Nageshwar, Eberhardt and/or Do in further view of J. Jiang et al., CN 105481744 (2016) (“Jiang”). Jiang teaches that dodecylmethylethanolamine is an intermediate useful to obtain CO2/N2-H2O2 dual-stimulation responsive surfactants according to the formula listed in Jiang paragraph [0006]. See Jiang at page 3, [0006]; Jiang at page 5, [0023]-[0026] (teaching synthesis of bis( dodecylmethyl)tertiary amine selenide from dodecylmethylethanolamine). Dodecylmethylethanolamine has the following structure:
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which meets the chemical structure variables of claim 19. Jiang teaches synthesis of dodecylmethylethanolamine by reacting 4-N-monometlylethanolamine with bromododecane. Jiang at page 4, [0021]-[0022]. Claim 19 is obvious because one of ordinary skill is motivated to prepare dodecylmethylethanolamine by reductive amination between 4-N-monometlylethanolamine and undecanal according to the procedure of any of Clendennen (Example 5), Nageshwar, Eberhardt and/or Do, within the instantly claimed temperature/pressure ranges for the same reasons as given for claim 18 above. One of ordinary skill is so motivated simply as an alternative, convenient synthesis of the useful dodecylmethylethanolamine.
Claim 20 is obvious over Clendennen because corresponding variable R2 in either of Clendennen working Examples 37 or 50 is methyl.
Conclusion
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ALEXANDER R. PAGANO
Examiner
Art Unit 1692
/ALEXANDER R PAGANO/Primary Examiner, Art Unit 1692
1 Room temperature in the art of chemistry generally means about 20 °C to about 25 °C. See e.g., Hawley's Condensed Chemical Dictionary, page 1201 (16th ed., 2016, R.J. Larrañaga ed.).
2 MPEP § 2144.04 (IV)(C) (citing Ex parte Rubin, 128 USPQ 440 (Bd. App. 1959) (Prior art reference disclosing a process of making a laminated sheet wherein a base sheet is first coated with a metallic film and thereafter impregnated with a thermosetting material was held to render prima facie obvious claims directed to a process of making a laminated sheet by reversing the order of the prior art process steps.). See also In re Burhans, 154 F.2d 690, 69 USPQ 330 (CCPA 1946) (selection of any order of performing process steps is prima facie obvious in the absence of new or unexpected results); In re Gibson, 39 F.2d 975, 5 USPQ 230 (CCPA 1930) (Selection of any order of mixing ingredients is prima facie obvious.).
3 The art teaches that radiocarbon analysis distinguishes between biobased carbon and fossil carbon by measuring the ratio of 14C and 12C isotopes in a sample. M. Haverly et al., 237 Fuel, 1108-1111 (2019) (see page 1108, col. 1). For example, ASTM D6866-12, Method B teaches the pMC (percent modern carbon (14C)), is calculated according to the following equation:
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See ASTM Designation: D6866-12 (2021). Fossil fuels (and chemicals produced therefrom, such as ethylene), although derived from living organisms, do not contain 14C. see e.g., C. Bettenhausen, Switching to sustainable surfactants, 100 Chem. Eng. News, 22-27 (2022). Presumably, this is because fossil fuels remain buried for millions of years where the 14C isotope has fully radioactively decayed, whereas the 14C isotope in modern biomass, from incorporation and metabolism of atmospheric 14CO2, has not yet fully decayed. The half-life of 14C is over 5000 years.
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