DETAILED ACTION
STATUS OF THE APPLICATION
Receipt is acknowledged of Applicants’ Amendments and Remarks, filed 6 March 2024, in the matter of Application No. 18/596,842. Said documents have been entered on the record. The Examiner further acknowledges the following:
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claims 1-4 are pending.
No claims have been amended.
No claims have been cancelled.
Thus, claims 1-4 represent all claims currently under consideration.
Priority
Acknowledgment is made of Applicants’ claim for foreign priority under 35 U.S.C. 119 (a)-(d). The certified copy has been filed in the present application filed on 6 March 2024. Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55. Applicant claims foreign priority to Application No. EP23160687.2, filed on 8 March 2023.
Foreign Applications:
EUROPEAN PATENT 23160687.2 (03/08/2023)
Information Disclosure Statement (IDS)
The information disclosure statement (IDS) submitted on 6 March 2024 is in compliance with the provisions of 37 CFR 1.97. Accordingly, the IDS is being considered by the Examiner.
Drawings
The drawings are objected to because in the legend for the x-axis of Figure 1, “pdoduct” should read “product”.
Corrected drawing sheets in compliance with 37 CFR 1.121(d) are required in reply to the Office action to avoid abandonment of the application. Any amended replacement drawing sheet should include all of the figures appearing on the immediate prior version of the sheet, even if only one figure is being amended. The figure or figure number of an amended drawing should not be labeled as “amended.” If a drawing figure is to be canceled, the appropriate figure must be removed from the replacement sheet, and where necessary, the remaining figures must be renumbered and appropriate changes made to the brief description of the several views of the drawings for consistency. Additional replacement sheets may be necessary to show the renumbering of the remaining figures. Each drawing sheet submitted after the filing date of an application must be labeled in the top margin as either “Replacement Sheet” or “New Sheet” pursuant to 37 CFR 1.121(d). If the changes are not accepted by the examiner, the applicant will be notified and informed of any required corrective action in the next Office action. The objection to the drawings will not be held in abeyance.
Specification
The disclosure is objected to because of the following informalities:
In Examples 1-6 (Specification; pages 6-7), “95÷100ºC” should read “95-100 ºC”
Appropriate correction is required.
Claim Objections
Claim 1 is objected to because of the following informalities:
In line 1, “A compounds of formula 1” should read “A compound of formula 1” or “Compounds of formula 1” (supported by the Specification; page 3, line 27 through page 4, line 6).
In line 2, the graphic representing formula 1 is blurry and difficult to read, especially the subscripted variable “n”.
In line 8, the word “or” should be placed between the penultimate and final options, after the appearance of “hydrogen;”.
In line 10, “CH2PO3M2.” should read “CH2PO3M2;”
Claim 2 is objected to because of the following informalities:
In line 4, the graphic representing the epoxide formula is blurry difficult to read, especially the subscripted number “6”.
In line 4, the formula representing the epoxide should be representing by a letter or a number (e.g., formula 2).
In line 7, “…phosphonomethyleting…” should read “…phosphonomethylating…”
Claim 4 is objected to because of the following informalities:
In line 2, “…vehicles, excipients…” should read “…vehicles, and excipients…”
Appropriate correction is required.
Claim Rejections - 35 USC § 112(b)
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 1-4 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 a genus of compounds represented by formula 1. However, the variable n is not defined, the only embodiments appears to be n = 0 to 1 based on claim 2, and this ambiguity is not adequately addressed in the written description (Specification; page 3, lines 1-12). Therefore, the scope of the instant claim is unclear and this ambiguity renders the instant claim indefinite. Further clarification is required. For the purposes of examination, the variable n will be interpreted as any number, including zero. Due to a lack of a definition of variable n in the written description, a broadest reasonable interpretation defining the variable n will be used as detailed above.
Regarding claims 2-4, these dependent claims do not resolve the indefiniteness of claim 1 detailed above.
Claim 2 recites a process for the preparation of the compounds of claim 1 comprising: a) reacting ethylenediamine or diethylenetriamine with a compound selected from: and epoxide of formula
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Wherein R6 is hydrogen, methyl, chloromethyl, or hydroxymethyl to obtain functionalized polyamines” in lines 1-6. However, reacting ethylenediamine or diethylenetriamine with an epoxide wherein R6 is methyl, chloromethyl, or hydroxymethyl would afford compounds with hydroxyethyl groups substituted with methyl, chloromethyl, or hydroxymethyl, respectively, and these compounds reside outside of the genus of claim 1 on with the instant claim depends because R and R1-R4 can only comprise hydroxyethyl (-CH2CH2OH), and does not comprise a substituted hydroxyethyl group. Therefore, in instances wherein R6 is methyl, chloromethyl, or hydroxymethyl, these corresponding compounds would be outside of the scope of formula 1 of claim 1 as recited. This ambiguity renders the instant claim indefinite. Further clarification is required. The Examiner notes that adequately addressing this ambiguity, for example if “hydroxyethyl” in claim 1 on which the instant claim depends were to read as “substituted or unsubstituted hydroxyethyl”, would ameliorate this claim rejection.
Claim 3 recites the phrase “A method of chelating and sequestering agents, precipitating inhibitors, dispersants, boosters in laundry detergents and anti-scale agents…” in lines 1-2. However, it is unclear as written what the method step of “adding said compounds to laundry detergents and anti-scale agents” to “dispersants, boosters in laundry detergents and antiscale agents” and this ambiguity renders the instant claim indefinite. The “booster effect” as defined in the written description appears to refer specifically boosting the cleaning performance in laundry detergents and not applicable to anti-scale agents or dispersants (c.f., Specification; page 4, lines 14-23; page 5, line 4; page 11, Example 2B). Further clarification is required. The Examiner notes that adequately addressing this ambiguity would ameliorate this claim rejection.
Claim Rejections - 35 USC § 102
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 the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
Claims 1 and 3-4 are rejected under 35 U.S.C. 102(a)(1) as anticipated by Molenaar et al. (DE 2505437 A1; published 08-28-1975; IDS of 03-06-2024; English language machine translation; hereinafter “Molenaar”).
Regarding claim 1 and claims 3-4 depending from claim 1, Molenaar discloses the use of polyamine compounds as universal plating agents for complexing copper that is sufficient to prevent the formation of free hydroxide precipitates based on phosphonic acid derivatives of polyamines (Molenaar; paragraphs [0006] and [0019]-[0022]; claims 1, 5, and 8; English language machine translation).
Of particular note, Example 7 of Molenaar discloses a composition comprising an aqueous solution of ferric ammonium sulfate, copper sulfate, and ethylenediamine-N,N’-hydroxyethyl-N,N’-dimethylphosphonic acid as a chelating agent and precipitation inhibitor (Molenaar; paragraphs [0119]-[0122]; Example 7; English language machine translation). The species disclosed by Molenaar anticipates formula 1 of instant claim 1 when R and R1 are -CH2PO3M2 wherein M is hydrogen; R3 and R4 are hydroxyethyl, and n is 0. Furthermore the formulation and method of Molenaar with the species of Example 7 anticipates the limitations of instant claims 3-4.
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 text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
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 and 3-4 are rejected under 35 U.S.C. 103 as being unpatentable over Paladini et al. (US 2005/0171376 A1; hereinafter “Paladini”).
Regarding claim 1, Paladini discloses polyaminomethylenephosphonate derivatives usable as inhibitors of precipitation and dispersants in aqueous systems for use in the water treatment and detergent fields (Paladini; Title; Abstract).
Paladini further discloses compounds of general formula
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where n is between 2 and 15000; M2 can be hydrogen or a suitable cation and each R group can be a —CH2PO3M2 group, or linear or branched alkyl residue resulting from the reaction of the terminal amine groups with the following reagent classes:
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where R1 can be H, CH3, CH2Cl, CH2OH;
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where R2 is an alkyl with a carbon atom number between 3 and 5; and
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where Z is a group chosen from: CONH2, CHO, COOR, COOX, where R═CH3, C2H5, and where X═H, Na, K, NH4 (Paladini; claim 1). The CH2PO3M2 group of Paladini is further defined as wherein M may be hydrogen or a suitable cation such as alkali metal of ammonium (Paladini; claim 2). The reaction of the terminal amine groups with the claimed epoxides (reagent class 1) of Paladini will produce the claimed products of instant claim 1.
Thus, the genus of Paladini comprises the compounds of formula 1 of instant claim 1 when R and R4 are -CH2PO3M2, wherein M is hydrogen, alkali metal, or ammonium; R1-R3 are hydroxyethyl groups (i.e., linear alkyl residues resulting from the reaction of the terminal amine groups with reagent class 1, wherein R1 is H); and when n is between 2 and 15000.
Further regarding claim 1, Example 1 of Paladini discloses the following:
Into a suitable reaction vessel 350-g of triethylenetetramine were charged; thereafter the reaction mixture was heated at 90-95° C. Ethylene oxide was then added stepwise at such a rate that, with external cooling applied, the temperature did not exceed 100° C. 211 g of ethylene oxide had been added over a period 1½ hours. The resultant product was then converted in the phosphonomethylated derivates according to Mannich's reaction. With the same synthetic path is possible to obtain β hydroxyethyl derivates of linear or branched polyamines or mixture of them in a right ratio (Paladini; paragraphs [0076]-[0079]; Example 1).
Paladini’s Example 1 reacts 2.39 moles triethylenetetramine (based on 350 g) with 4.79 moles of ethylene oxide (based on 211 g) at a temperature not exceeding 100 ºC. This further corresponds to 2 moles of ethylene oxide per mole of polyamine and 0.5 moles ethylene oxide per reactive N atom of the polyamine reactant. Furthermore, Example 2 of the present application reacts 4.79 moles of diethylenetriamine (based on 495 g) with 4.77 moles of ethylene oxide (based on 210 g) at a temperature not exceeding 110 ºC (Specification; page 6, lines 10-15). This further corresponds to 1 mole of ethylene oxide per mole of polyamine and 0.33 moles ethylene oxide per reactive N atom of the polyamine reactant. Thus, using the reaction conditions of Paladini, which are substantially similar to that of the present application, would be expected to afford a mixture of N-hydroxyethylated compounds with substitution patterns consistent with formula 1 of instant claim 1 when n is 2 (i.e., R2, R3, and R4 are hydroxyethyl; R1, R2, and R3 are hydroxyethyl; R1, R3, and R4 are hydroxyethyl; R2 and R3 are hydroxyethyl; and R, R3, and R4 are hydroxyethyl). The a majority of the unreacted free -NH sites in the products following Paladini’s Example 1 will be available for phosphonomethylation in the following step, as detailed below.
Example 4 of Paladini discloses the phosphonomethylation of the products of Paladini’s Example 1 as follows:
Into a suitable reaction vessel 234 g of compound of example 1 were added to a 70% phosphorous acid solution (478 g) and 32% of hydrochloric acid (342 g). The mixture thus obtained was heated to reflux, 340 g of 37% aqueous formaldehyde solution was added phosphorous acid solution (478 g) and 32% of hydrochloric acid (342 g). The mixture thus obtained was heated to reflux, 340 g of 37%, aqueous formaldehyde solution was added dropwise in the course of ca 1 hr and the reaction mixture was kept at reflux temperature for 1 additional hr. 300 g volatiles substances was then removed from the reaction mixture by distillation. The final product obtained was a viscous fluid having an active substance of 50%. Infrared analysis of the product showed the presence of methylenephosphonic amine groups, while P31 NMR analysis indicate that at least 90% of the amine groups had been phosphonomethylated. The impurities include unreacted phosphorous acid, phosphoric acid and other unidentified compounds (Paladini; paragraph [0088]; Example 4).
Similarly, Example 9 of the present application reacts the compounds of Example 1 (320-335 g) with a 70% phosphorous acid solution (1070-1120 g) and a 32% hydrochloric acid solution (640-670 g). The reaction mixture was heated to reflux and reacted with paraformaldehyde (320-330 g) which was added over 1.5 h and stirred for an additional 3 h. The volatiles were removed and the final product obtained was a viscous fluid having an active substance of 50%. IR analysis of the product showed the presence of methylenephosphonic amine groups, while IC analysis indicated that at least 90% of phosphorous acid has reacted (Specification; page 8, lines 9-19, Example 9). Example 10 of the present application also indicates that 45% formaldehyde solution can be used as an alternative to paraformaldehyde (Specification; page 8, line 23, Example 10).
The method steps of Examples 1 and 4 of Paladini using triethylenetetramine starting material are substantially identical with the method steps of Examples 1-5 and 7-10 of the instant application that uses either diethylenetriamine or ethylenediamine as starting materials in terms of reactant stoichiometry, reaction temperatures, and the extent of methylenephosphonylation in the second method step (ca. 90%), respectively (Specification; pages 6-8; Examples 1-5 and 7-10).
Since the reaction products of Paladini’s Example 1 are expected to produce a mixture of N-hydroxylated compounds wherein 0.5 of the N atoms per mole are hydroxyethylated, as detailed above, and Paladini’s Example 4 indicates that at least 90% of the amine groups are phosphonomethylated, the species of Paladini’s Example 4 are expected to be a mixture of mono- and bis-phosphonylmethylated species, with some free amino groups (-NH) remaining. Therefore, based on the teachings of Paladini, the skilled artisan could predictably obtain at least a compound mixture of formula 1 of instant claim 1 when n is 2 and M is hydrogen, wherein at least R and R4 are -CH2POM2 and the other R are hydroxyethyl, hydrogen or -CH2PO3M2, and M is hydrogen, an alkali metal, or ammonium with a reasonable expectation of success.
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have arrived at compounds represented by formula 1 of instant claim 1 with a reasonable expectation of success, because the reaction conditions of Examples 1 and 4 of Example 4 of Paladini are substantially similar to that of the present application, Paladini explicitly teaches the preparation of at least two species that reside within the genus of formula 1 of instant claim 1 when n is 2 and M is hydrogen. Furthermore, for compounds not readily obtainable of Examples 1 and 4 of Paladini, the genus of Paladini encompasses them and could be obtained through routine optimization of the reaction conditions, for example by varying the reaction time from 1 to 5 h (Paladini; paragraph [0072]).
Regarding claim 3 depending from claim 1, Paladini discloses the use of polyaminomethylenephosphonate derivatives as scale inhibitors, chelating and sequestering agents, corrosion inhibitors (Paladini; paragraphs [0016] and [0049]-[0050]; claims 5-7). Paladini further discloses that the new additives prevent the segregation of solids from their aqueous solutions or dispersions acting as precipitation inhibitors and dispersants (Paladini; paragraphs [0001], [0048], and [0052]). In addition, Paladini discloses that products according to the invention can be used in laundry detergents (Paladini; paragraphs [0053] and [0067]).
Regarding claim 4 depending from claim 1, Paladini teaches the use of the polyaminomethylene phosphonate derivative of Example 4 as a dispersing agent present in substoichiometric amounts to inhibit the precipitation of solutions supersaturated with calcium carbonate in deionized water (Paladini; paragraphs [0101]-[0105]; Example 5; Table 1); as an iron sequestering agent in an aqueous solution of ferric ions (Paladini; paragraphs [0114]-[0116]; Example 11; Table 9) and as a corrosion inhibitor in an aqueous solution of NaOH with steel coupons (Paladini; paragraphs [0122]-[0127]; Example 12; Table 10).
Claim 2 is rejected under 35 U.S.C. 103 as being unpatentable over Paladini et al. (US 2005/0171376 A1; hereinafter “Paladini”) as applied to claims 1 and 3-4 above, and further in view of Molenaar et al. (DE 2505437 A1; IDS of 03-06-2024; English language machine translation; hereinafter “Molenaar”).
Regarding claim 2, claim 1 is rendered obvious over Paladini as detailed above.
Examples 1 and 4 of Paladini teach the reaction of triethylenetetramine with ethylene oxide and a subsequent phosphonomethylating method step of the compounds of Example 1 by reaction in an aqueous solution of phosphorous acid and formaldehyde in the presence of hydrochloric acid (Paladini; paragraphs [0076]-[0079] and [0088]; Examples 1 and 4). Ethylene oxide corresponds to the epoxide formula of instant claim 2 when R6 is hydrogen.
In addition, claim 1 of Paladini teaches that the compounds of Paladini can be reacted with the following reagent class:
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where R1 can be H, CH3, CH2Cl, CH2OH (Paladini; claim 1). The genus of reagent class 1 of Paladini is identical to the instantly claimed genus of the epoxide formula of instant claim 2.
Paladini fails to explicitly teach reacting ethylenediamine or diethylenetriamine, as recited in instant claim 2.
However, the triethylenetetramine disclosed in Example 1 of Paladini is a structurally similar polyamine compound that differs from either of ethylenediamine or diethylenetriamine by 1 or 2 monomeric -NRCH2CH2- units, respectively, and are therefore deemed homologs. MPEP § 2144.09(II) states that “Compounds which are position isomers (compounds having the same radicals in physically different positions on the same nucleus) or homologs (compounds differing regularly by the successive addition of the same chemical group, e.g., by -CH2- groups) are generally of sufficiently close structural similarity that there is a presumed expectation that such compounds possess similar properties.” In the instant case, a rejection based on closed structural similarity is founded on the expectation that compounds similar in structure will have similar properties.
Furthermore, Molenaar discloses the use of polyamine compounds as universal plating agents for complexing copper that is sufficient to prevent the formation of free hydroxide precipitates based on phosphonic acid derivatives of polyamines (Molenaar; paragraphs [0006] and [0019]-[0022]; claims 1, 5, and 8; English language machine translation).
Of particular note, Example 7 of Molenaar discloses a composition comprising an aqueous solution of ferric ammonium sulfate, copper sulfate, and ethylenediamine-N,N’-hydroxyethyl-N,N’-dimethylphosphonic acid as a chelating agent and precipitation inhibitor (Molenaar; paragraphs [0119]-[0122]; Example 7; English language machine translation). The species disclosed by Molenaar anticipates formula 1 of instant claim 1 when R and R1 are -CH2PO3M2 wherein M is hydrogen; R3 and R4 are hydroxyethyl, and n is 0, as detailed above.
It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified Paladini to incorporate the teachings of Molenaar to substitute the use of triethylenetetramine in the method of Paladini with ethylenediamine as taught by Molenaar with a reasonable expectation of success, because Molenaar teaches a phosphonomethylated amine of formula 1 of claim 1 derived from ethylenediamine, both Paladini and Molenaar teach the use of structural homologs (i.e., phosphonomethylated polyamines differing by a single monomeric unit) with overlapping utility as chelating agents and precipitating inhibitors, and therefore the reaction to produce the compounds of Molenaar using the process of Paladini is predictable. Also see MPEP § 2143(I)(B).
Based on the combined teachings of the references, the Examiner submits that a person of ordinary skill in the art would have had a reasonable expectation of success of arriving at the instantly claimed method. Therefore, the invention as a whole would have been prima facie obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, and absent a clear showing of evidence to the contrary.
Conclusion
Any inquiry concerning this communication or earlier communications from the Examiner should be directed to Derek Rhoades whose telephone number is (703)-756-5321. The Examiner can normally be reached Monday–Thursday, 7:30 am–5:00 pm EST; Friday, 7:30 am–4:00 pm EST.
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/D.R./Examiner, Art Unit 1692
/AMY C BONAPARTE/Primary Examiner, Art Unit 1692
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