Use of anthranilic acid in the preparation of compounds of interest

Abstract

The present invention relates to the use of anthranilic acid in a process for preparing a compound selected from copper phthalocyanine, quinacridone, 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide (PY74), and 2-({2-oxo-1-[(2-oxo-2,3-dihydro-1H-benzimidazole-5-yl)carbamoyl]propyl}diazenyl)benzoic acid (PY151). In particular, the anthranilic acid is produced or obtained from a microorganism.

Description

[0001] USE OF ANTHRANILIC ACID IN THE PREPARATION OF COMPOUNDS OF INTEREST

[0002] SUBJECT OF THE INVENTION

[0003] The present invention relates to the synthesis of compounds or molecules of interest in various fields, mainly in the field of dyes and pigments, from a common precursor, anthranilic acid.

[0004] BACKGROUND OF THE INVENTION

[0005] For decades, many products have been developed for use as precursors or reaction intermediates in the industrial-scale synthesis of dyes and pigments. Among these products or compounds, we can mention copper phthalocyanine (CAS No. 147-14-8, also known as phthalocyanine blue, "PB15:3"), quinacridone (CAS No. 1047-16-1, also known as Pigment Violet 19, "PV19", 5,12-Dihydroquin[2,3-b]acridine-7,14-dione), 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutaname (CAS No. 6358-31-2, also known as 2-[(2-methoxy-4-nitrophenyl)azo]-N-(2-methoxyphenyl)-3-oxobutaname, "PY74"), and 2- ({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid (CAS No.: 31837-42-0, also known as 2-[[l-[[(2,3-dihydro-2-oxo-lH-benzimidazol-5-yl)amino]carbonyl]-2-oxopropyl]azo]benzoic acid, "PY151").

[0006] Copper phthalocyanine is a standard pigment used in inks, coatings, and plastics. It is characterized by its brilliant blue color and is among the most widely produced pigments globally. Industrially, copper phthalocyanine is primarily obtained using two methods (Lôbbert, G. Phthalocyanines. In Ullmann's Encyclopedia of Industrial Chemistry; John Wiley & Sons, Ltd, 2000). Both methods involve heating either phthalic anhydride or phthalonitrile to a temperature above 200 °C in the presence of a copper salt and optionally a catalyst. The phthalic anhydride intermediate can be prepared from the gas-phase oxidation of naphthalene in the presence of a vanadium catalyst. This can then be hydrolyzed into phthalic acid, converted into phthalimide, and then dehydrated to give the intermediate phthalonitrile (P.Lortz et al, Phthalic Acid and Derivatives, Ullman’s Encyclopedia of Industrial Chemistry, Wiley, 2012.).

[0007] Quinacridone PV19 is an important red pigment in the dye industry due to its stability and excellent resistance to light and weathering. This is why it is widely used in industrial and automotive paints, coatings, plastics, and inks. In conventional quinacridone synthesis, benzene and butane, derived from fossil resources, are the main raw materials. The process developed in 1955 by DuPont remains industrially important for the synthesis of quinacridone (Hunger, K.; Herbst, W. Pigments, Organic. In Ullmann's Encyclopedia of Industrial Chemistry; John Wiley & Sons, Ltd, 2000). More specifically, the succinosuccinate ester, obtained from the corresponding succinate, is reacted with an aromatic amine (aniline, p- or m-toluidine, 4- or 3-chloroaniline) to form the dihydroterephthalic diester.The latter can be directly converted to dihydroquinacridone by thermal intramolecular cyclization in the same reaction medium at 250 °C. The dihydroquinacridone is then oxidized in aqueous medium to form quinacridone.

[0008] 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanametamide (PY74) is a yellow pigment used in the ink and plastics industries. Due to the presence of an azo functional group, it is classified as an azo dye, which accounts for more than 50% of all commercial dyes. The industrial synthesis route involves azo coupling between the diazonium salt of 5-nitro-2-aminoanisole and o-acetoacetanisidide by heating the mixture in a basic medium (EP 1,424,370 and US 4,457,783). This synthesis route results in PY74 containing a variety of toxic or carcinogenic aromatic amine impurities that are difficult to remove. Furthermore, this route uses anisidine as a raw material obtained industrially by the reduction of nitroanisole (CN 103073436). However, this anisidine synthesis route generates byproducts that are difficult to separate and produces a considerable amount of aqueous waste.

[0009] 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid (PY151) is a yellow pigment belonging to the monoazo compound family, primarily used in the ink and plastic polymer industries. PY151 is commonly obtained by azo coupling of the diazonium salt derived from anthranilic acid with 5-N-acetoacetylaminobenzimidazolone (Hunger, K.; Herbst, W. Pigments, Organic. In Ullmann's Encyclopedia of Industrial Chemistry; John Wiley & Sons, Ltd, 2000.). The latter is itself obtained by reacting the acetoacetic acid ester or diketene with 5-aminobenzimidazolone. However, current industrial synthesis methods for 5-aminobenzimidazole and its precursor, benzimidazolone, still need improvement. Indeed, at present, they rely on the use of urea or phosgene on orthophenylenediamine under extreme pressure and temperature conditions (CN 117447405).They use organic solvents and harmful reagents (phosgene), and generate a large amount of waste and corrosive reaction by-products (HCl). Finally, yields are often low and are obtained through energy-intensive processes.

[0010] The industrial synthesis of these four pigments and their main intermediates is currently achieved through industrial processes based on conventional chemistry, which does not always take sustainable development issues into account. However, reducing carbon dioxide emissions has become crucial, as has the shift from petroleum-derived raw materials to renewable / bio-based raw materials. Furthermore, replacing toxic chemicals with less toxic alternatives is essential.

[0011] Current industrial production processes for these four pigments of interest to the dye industry are not satisfactory with regard to present and future environmental requirements.

[0012] There therefore remains a real need to develop and make available improved processes for preparing these compounds of interest that are simple, efficient, ecological, safe, and well suited to industrial level.

[0013] SUMMARY OF THE INVENTION

[0014] In this context, the inventors proposed various industrially adapted and more environmentally friendly preparation processes for the four pigments of interest: copper phthalocyanine, quinacridone, 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutaamide (PY74), and 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid (PY151) from a common intermediate compound, anthranilic acid. Thus, the present invention relates to the use of anthranilic acid in a process for preparing a compound selected from copper phthalocyanine, quinacridone, 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide, and 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid.

[0015] One aspect of the invention is the use of anthranilic acid in a process for preparing copper phthalocyanine.

[0016] According to this aspect, the process includes the following steps: a1) reacting anthranilic acid with sodium nitrite and sulfuric acid in aqueous solution, followed by the addition of a cyanide salt to obtain 2-cyanobenzoic acid; a2) reacting 2-cyanobenzoic acid with copper chloride, urea, and ammonium molybdate in a solvent; and a3) recovering copper phthalocyanine.

[0017] In particular, step a1) includes reacting anthranilic acid with sodium nitrite and sulfuric acid in aqueous solution followed by the addition of a mixture of sodium cyanide and copper cyanide at a temperature of about 0 °C; and step a2) includes reacting 2-cyanobenzoic acid with copper chloride, urea, and ammonium molybdate in anisole at a temperature between 100 and 200 °C, for 8 to 24 hours.

[0018] An object of the invention is also the use of anthranilic acid in a process for preparing 2-cyanobenzoic acid, said process comprising the following steps: a) reacting anthranilic acid with sodium nitrite and sulfuric acid in an aqueous solution, followed by the addition of a cyanide salt, in particular a mixture of sodium cyanide and copper cyanide, preferably at a temperature of about 0 °C; and a') recovering 2-cyanobenzoic acid.

[0019] Another aspect of the invention is the use of anthranilic acid in a process for preparing quinacridone.

[0020] According to this aspect, the process includes the following steps: b1) reacting anthranilic acid with benzoquinone to obtain 2,2'-((3,6-dioxocyclohexa-l,4-diene-l,4-diyl)bis(azanediyl))dibenzoic acid; b2) reacting 2,2'-((3,6-dioxocyclohexa-l,4-diene-l,4-diyl)bis(azanediyl))dibenzoic acid with phosphoric anhydride to obtain quinacridonequinone; b3) reacting quinacridonequinone with zinc to obtain 6,13-dihydroquinacridone; b4) reacting 6,13-dihydroquinacridone with sodium 3-nitrobenzenesulfonate; and b5) recovering quinacridone.

[0021] In particular, step bl) includes reacting anthranilic acid with benzoquinone in a solvent at a temperature between 50 and 100 °C, for 12 to 24 hours; and step b2) includes reacting 2,2'-((3,6-dioxocyclohexa-l,4-diene-l,4-diyl)bis(azanediyl))dibenzoic acid in a mixture of trifluoroacetic acid and methanesulfonic acid with phosphoric anhydride at a temperature between 40 and 100 °C, for 12 to 24 hours.

[0022] Another aspect of the invention is the use of anthranilic acid in a process for preparing 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutamid.

[0023] According to this aspect, the process comprises the following steps: c1) obtaining o-anisidine from anthranilic acid; c2) obtaining p-nitro-o-anisidine from o-anisidine; c3) obtaining N-(2-methoxyphenyl)-3-oxobutanamide from o-anisidine; c4) obtaining 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide by coupling p-nitro-o-anisidine with N-(2-methoxyphenyl)-3-oxobutanamide; and c5) recovering 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide.

[0024] In particular, which step c1) comprises the following steps: c1a) reacting anthranilic acid with sulfuric acid and a sodium nitrite solution at a temperature between 90 and 130 °C for 5 to 60 minutes to obtain salicylic acid; c1b) reacting salicylic acid with potassium carbonate and dimethyl sulfate at a temperature between 40 and 80 °C for 12 to 24 hours to obtain methyl 2-methoxybenzoate; c1c) reacting methyl 2-methoxybenzoate with hydroxylamine and potassium hydroxide to obtain N-hydroxy-2-methoxybenzamide; cld) the reaction of N-hydroxy-2-methoxybenzamide with potassium carbonate and acetic anhydride at a temperature between 70 and 110 °C for 2 to 6 hours i and cle) the recovery of o-anisidine.

[0025] In particular, step c2) includes the following steps: c2a) reacting o-anisidine with acetic acid at a temperature between 90 and 140 °C for 12 to 20 hours to obtain N-(2-methoxyphenyl)acetamide; c2b) reacting N-(2-methoxyphenyl)acetamide with acetic anhydride and nitric acid at a temperature between 20 and 40 °C to obtain N-(2-methoxy-4-nitrophenyl)acetamide; and c2c) reacting N-(2-methoxy-4-nitrophenyl)acetamide in sodium hydroxide solution at a temperature between 70 and 110 °C for 12 to 24 hours; and c2d) recovering p-nitro-o-anisidine.

[0026] Specifically, step c3) includes reacting o-anisidine with ethyl acetoacetate and pyridine at a temperature between 90 and 130 °C for 12 to 20 hours. Specifically, step c4) includes reacting an aqueous solution of p-nitro-o-anisidine and sodium nitrite with an aqueous solution of N-(2-methoxyphenyl)-3-oxobutanamide at a temperature between 15 and 25 °C for 1 to 6 hours.

[0027] Another aspect of the invention is the use of anthranilic acid in a process for preparing 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid.

[0028] According to this aspect, the process includes the following steps: d1) obtaining 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one from anthranilic acid; and d2) reacting 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one with the diazonium salt of anthranilic acid; and d3) recovering 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid.

[0029] In particular, step dl) includes the following steps: dla) reacting anthranilic acid with sulfuric acid in a solvent under reflux for 12 to 20 hours, preferably about 16 hours, to obtain methyl anthranilate; dlb) reacting methyl anthranilate with bis(hydroxylammonium) sulfate and followed by the addition of a sodium sulfite solution to obtain hydroxamic anthranilic acid; dlc) reacting hydroxamic anthranilic acid with ethyl chloride oformiate in a basic solution at a temperature between 10 and 35 °C, preferably about 20 °C, for 1 to 4 hours, preferably about two hours, to obtain 1,3-dihydrobenzimidazol-2-one;did) the reaction of 1,3-dihydrobenzimidazol-2-one with sulfuric acid and nitric acid at a temperature between 0 and 15 °C, preferably about 5 °C to obtain 5-nitro-1,3-dihydrobenzimidazol-2-one; die) the reaction of 5-nitro-1,3-dihydrobenzimidazol-2-one with palladium on carbon and ammonium formate in a solvent for 30 minutes to 12 hours, preferably about 1 hour to obtain 5-amino-1,3-dihydrobenzimidazol-2-one; dlf) the reaction of 5-amino-1,3-dihydrobenzimidazol-2-one with 2,2,6-trimethyl-4H-1,3-dioxine-4-one in refluxing water for 30 minutes to 3 hours; and dig) the recovery of 5-acetoacetamido-l-3-dihydrobenzimidazol-2-one.;

[0030] An object of the invention is also the use of anthranilic acid in a process for preparing 1,3-dihydrobenzimidazol-2-one, said process comprising the following steps: dla) reacting anthranilic acid with sulfuric acid in a solvent under reflux for 12 to 20 hours, preferably about 16 hours, to obtain methyl anthranilate; dlb) reacting methyl anthranilate with bis(hydroxylammonium) sulfate and followed by the addition of a sodium sulfite solution to obtain hydroxamic anthranilic acid; dlc) the reaction of hydroxamic anthranilic acid with ethyl chloroformiate in a basic solution at a temperature between 10 and 35 °C, preferably about 20 °C, for 1 to 4 hours, preferably about two hours to obtain 1,3-dihydrobenzimidazol-2-one; and dl') the recovery of 1,3-dihydrobenzimidazol-2-one.According to a particular embodiment of the invention, anthranilic acid is produced from a microorganism, in particular a bacterium, preferably of the species Escherichia coli.

[0031] An additional object of the invention relates to copper phthalocyanine comprising a percentage of modern carbon equal to or greater than 80%, preferably equal to or greater than

[0032] 87.5%, or even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640.

[0033] Another additional object of the invention for 2-cyanobenzoic acid comprising a percentage of modern carbon equal to or greater than 70%, preferably equal to or greater than 80%, even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640.

[0034] Another additional object of the invention relates to quinacridone comprising a percentage of modern carbon equal to or greater than 60%, preferably equal to or greater than 70%, even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640.

[0035] Another additional object of the invention relates to 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanametamide comprising a percentage of modern carbon equal to or greater than 60%, preferably equal to or greater than 66.5%, preferably equal to or greater than 77.5%, and even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640.

[0036] Another additional object of the invention relates to 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid comprising a percentage of modern carbon equal to or greater than 60%, preferably equal to or greater than

[0037] 77.5%, and even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640. Another additional object of the invention relates to 1,3-Dihydrobenzimidazol-2-one comprising a percentage of modern carbon equal to or greater than 90%, preferably equal to or greater than 95%, and even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640.

[0038] DETAILED DESCRIPTION

[0039] In this application, the term "approximately" associated with a value is a term well known to those skilled in the art and means that said value may vary to some extent depending on the context in which the term is used. If some uses of this term are not clear to those skilled in the art depending on the context, then "approximately" means plus or minus 30%, plus or minus 20%, preferably plus or minus 10% of said associated value.

[0040] Unless otherwise stated, when a range is expressed using the phrase "between", the limit values ​​are included within the range described.

[0041] According to the invention, the terms "includes" or "comprising" can be interpreted generally as meaning that all specifically mentioned features and all optional, additional, and unspecified features are included. They can also be interpreted more specifically, as with the expressions "consists of" or "consisting of," when only the specified features are included, unless otherwise indicated.

[0042] As used here, the term "microorganism" is a unicellular organism that may be a bacterium, such as Escherichia coli. In a particular mode, the term "microorganism" also includes a "recombinant microorganism." By "recombinant microorganism," we mean a microorganism that is not found in nature and that contains a modified genome resulting from the insertion, modification, or deletion of one or more genetic elements. This term also includes any offspring of said microorganism that are not identical to the parent microorganism due to mutations that occur during replication. In a preferred mode, the microorganism is a bacterium, specifically Escherichia coli (E. coli).The present invention relates to the use of anthranilic acid in a process for preparing a compound selected from copper phthalocyanine, quinacridone, 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanametamide, and 2-({2-oxo-1-[(2-oxo-2,3-dihydro-1H-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid. It therefore concerns a process for preparing these four compounds and their synthetic intermediates using anthranilic acid, particularly as a starting material for the reaction syntheses.

[0043] Anthranilic acid, or 2-aminobenzoic acid, is an organic compound with the following formula:

[0044] It is biosynthesized from chorismic acid and is a precursor of the amino acid tryptophan.

[0045] In the context of the invention, anthranilic acid can come from multiple sources. It can easily be chemically synthesized by a person skilled in the art and with general knowledge, or simply purchased from various suppliers.

[0046] Alternatively, it can be obtained through biological processes using microorganisms that are much more ecologically sound. According to this alternative, anthranilic acid has a bio-based carbon content of at least 90%, in particular at least 99%, and preferably 100%.

[0047] The determination of the bio-based carbon content of a compound or molecule can be determined by any method known to a person skilled in the art from the measurement of the carbon content 14 ( 14C) In particular, it can be determined by accelerator mass spectrometry (AMS) according to standard NF EN 16640 published on April 15, 2017. The unit is the percentage of modern carbon (pMC). The pMC represents the ratio between the concentration of carbon-14 ( 14 C) in the analyzed molecule and the concentration of carbon 14 ( 14 C) in standardized modern carbon. The pMC thus corresponds to the percentage of bio-based carbon derived from biomass relative to fossil carbon (derived from petrochemicals). Therefore, a compound with 100% bio-based carbon content has a pMC of 100%. Conversely, a compound entirely of fossil origin, i.e., with 0% bio-based carbon content, has a pMC of 0%. A value between 0 and 100% indicates a mixture of bio-based and fossil carbon.

[0048] Annex E of standard NF EN 16640 describes a procedure for determining the content of 14C by SMA in carbonate solutions obtained from the combustion of bio-based product samples in a bomb calorimeter, tube furnace, or laboratory combustion device. More specifically, this procedure includes the following steps: a) Transfer the carbonate solution to the extraction bottle. b) Attach the HCl dosing device. c) Vacuum the bottle and dosing device (degassing, removing dissolved N2 and FO2 from the air). d) Add HCl to the carbonate solution. e) Remove water vapor using a trap filled with acetone and dry ice. f) Collect the CO2 formed in a trap immersed in liquid N2. g) Take a small sample to determine the 13 C at this stage. h) Transfer the CO2 to the graphitization system.

[0049] The gaseous sample must either be introduced into the system via a quartz tube or trapped in liquid nitrogen and then heated. The gas must then be converted into graphite using an iron catalyst according to the following formulas:

[0050] CO2 + H2 <- H2O + CO

[0051] CO + H2H2O + (ci) Remove the water produced by this reaction to ensure complete reduction to graphite. This step is particularly important to avoid any fractionation. (j) Compress the graphite into a target and mount it on a wheel before loading it into the accelerator mass spectrometer. In the ion source, a high-intensity beam of cesium ions (Cs +) is focused on the target. This operation releases negatively charged target atoms, producing a 36 keV beam of C' ions. The targets are kept 10 mm apart to prevent mutual contamination and moved during sputtering to avoid crater formation, which causes fractionation. The negative ion beam is then focused by a lens in a recombiner. In the recombiner, a series of magnets removes ions other than carbon ions from the beam and separates the three carbon isotopes ( 12 C, 13 This 14 C) Next, the chopper wheel physically blocks most of the 12 C, which allows the recombination of a very reduced carbon ion beam for simultaneous injection into the accelerator. k) In the tandem accelerator, the C' ions are accelerated to the terminal (to +2.5 MeV), then changed into C ions 3+by collision with Ar atoms in the degasser. These positive ions are accelerated to 10 MeV. A 3+ charge state is chosen because the mass / charge ratio of the 14 C 3+ is truly unique, which allows for its precise separation in the high-energy mass spectrometer. l) Measure the beams of 12 C and of 13 C in Faraday ionization chambers (typical currents of 250 nA). m) Purify the ions 14 C 3+ by an electrostatic deflector and a 90° magnet. They are measured in an ionization chamber filled with isobutene, isolated from the accelerator vacuum by a thin metal sheet. Generally, a sample is counted for one hour.

[0052] The isotopic ratios of 14 C / 12 This 13 C / 12C are determined relative to the appropriate primary reference material. All percentage modern carbon (pMC) values ​​obtained from radiocarbon analysis measurements must be corrected for isotopic fractionation using stable isotope data (ratios 13 C / 12 C) obtained on CO2 from the combustion of the sample.

[0053] The SMA system allows the measurement of carbon isotopes 12 C, 13 This 14 C of a carbon sample during the same sample analysis cycle. A sample lot must also contain samples of the reference material. The measured quantity of 14 C (= isotope concentration) 14 C) in a sample is calculated based on the measured quantity (average) of 14C. Reference material samples in the same lot. If the reference material is the primary reference standard, oxalic acid II (HOx-II, SRM 4990c), which is commonly used for this purpose, the standardized amount of 14 C in the sample, , Or

[0054] 14 Sample C represents the measured value of 14 C (in pMC) of the CO2 sample studied, u Sample represents the measured signal of the 14 C (isotopic concentration or activity) of the sample, 14 Ab g represents the measured signal of the 14 C (isotopic concentration or activity) of the reference sample / control sample, measured in the same batch as the sample and representing the background noise signal of the 14 C of the measured samples,

[0055] 14 Aox2 represents the measured (average) signal of the 14C (concentration or isotopic activity) of the reference standard samples, oxalic acid (HOx-II, SRM 4990c), measured in the same batch as the unknown samples,

[0056] 14 Ab g ox2 represents the measured (average) signal of the 14 C (concentration or isotopic activity) of the reference samples, which represents the background noise signal of the measured reference standard, oxalic acid (HOx-II, SRM 4990c), measured in the same batch as the oxalic acid samples, î]measurement represents the measurement efficiency of the measurement technique used, l 3 ô\- represents the standardized value of isotopic fractionation: l 3 ô\- = - 0.025 (relative to VPDB),

[0057] "^sample represents the measured value of the isotopic fractionation of the sample. It is obtained by measuring the ratio 13 C / 12 C of the sample as a function of the ratio 13 C / 12C measured from a reference standard having a known isotopic fractionation value associated with VPDB, and n ôox2 represents the standardized value of the isotopic fractionation of the reference standard, oxalic acid (HOx-II, SRM 4990c): u ôox2 = 0.0176 (relative to VPDB).

[0058] Preferably, the anthranilic acid is produced from a microorganism, in particular a bacterium, preferably of the species Escherichia coli. According to a specific method, the anthranilic acid produced from a microorganism, in particular a bacterium, preferably of the species Escherichia coli, has a percentage of modern carbon equal to or greater than 90%, preferably equal to or greater than 99%, and even more preferably 100%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640 as described above. In other words, the anthranilic acid produced from a microorganism, in particular a bacterium, preferably of the species Escherichia coli, has a bio-based carbon content equal to or greater than 90%, preferably equal to or greater than 99%, and even more preferably 100%.

[0059] According to one aspect of the invention, anthranilic acid is used in a process for preparing copper phthalocyanine. Preferably, anthranilic acid is used in a process for preparing copper phthalocyanine as described in this application. More particularly, the amine function of anthranilic acid is substituted with a cyano group via a Sandmeyer reaction, followed by tetrameric cyclization to provide copper phthalocyanine (PB 15:3).

[0060] An object of the invention therefore relates to a process or method for preparing copper phthalocyanine comprising the following steps: a1) reacting anthranilic acid with sodium nitrite and sulfuric acid in an aqueous solution, followed by the addition of a cyanide salt to obtain 2-cyanobenzoic acid; a2) reacting 2-cyanobenzoic acid with copper chloride, urea, and ammonium molybdate in a solvent; and a3) recovering copper phthalocyanine.

[0061] An object of the invention also relates to a process or method for preparing copper phthalocyanine consisting of the following steps: a1) reacting anthranilic acid with sodium nitrite and sulfuric acid in aqueous solution, followed by the addition of a cyanide salt to obtain 2-cyanobenzoic acid; a2) reacting 2-cyanobenzoic acid with copper chloride, urea, and ammonium molybdate in a solvent; and a3) recovering copper phthalocyanine.

[0062] Step a1) comprises a diazotization reaction followed by a cyanation reaction of anthranilic acid. In one particular embodiment, step a1) comprises reacting anthranilic acid with sodium nitrite and hydrochloric acid in aqueous solution, followed by the addition of a mixture of sodium cyanide and copper cyanide at a temperature of approximately 0 °C. This step a1) yields 2-cyanobenzoic acid.

[0063] Step a2) comprises the tetrameric cyclization of 2-cyanobenzoic acid. In one particular embodiment, step a2) comprises reacting 2-cyanobenzoic acid with copper chloride, urea, and ammonium molybdate in anisole at a temperature between 100 and 200 °C for 8 to 24 hours. Preferably, step a2) is carried out at a temperature between 120 and 180 °C, 140 and 160 °C, 150 and 160 °C, and even more preferably at a temperature of about 155 °C. Preferably, step a2) is carried out for 12 to 20 hours, 14 to 18 hours, and even more preferably for about 16 hours.

[0064] An object is therefore a process or method for preparing copper phthalocyanine comprising or consisting of the following steps: a1) reacting anthranilic acid with sodium nitrite and sulfuric acid in aqueous solution, followed by the addition of a mixture of sodium cyanide and copper cyanide at a temperature of about 0 °C to provide 2-cyanobenzoic acid; a2) reacting 2-cyanobenzoic acid with copper chloride, urea, and ammonium molybdate in anisole at a temperature between 100 and 200 °C, preferably about 155 °C, for 8 to 24 hours, preferably about 16 hours; and a3) recovering copper phthalocyanine.

[0065] In particular, anthranilic acid is produced or obtained by a biological process from a microorganism, in particular a bacterium, preferably of the species Escherichia Coli.

[0066] A particular object of the invention is therefore a process or method for preparing copper phthalocyanine comprising or consisting of the following steps: a) the culture of a microorganism as described in this application to produce anthranilic acid; and steps a1), a2), and a3) as described in this application.

[0067] A particular object of the invention is also a process or method for preparing copper phthalocyanine comprising or consisting of the following steps: a) culturing a microorganism as described in this application to produce anthranilic acid; a) reacting anthranilic acid with sodium nitrite and sulfuric acid in aqueous solution followed by the addition of a mixture of sodium cyanide and copper cyanide at a temperature of about 0 °C to provide 2-cyanobenzoic acid; a2) reacting 2-cyanobenzoic acid with copper chloride, urea, and ammonium molybdate in anisole at a temperature between 100 and 200 °C, preferably about 155 °C, for 8 to 24 hours, preferably about 16 hours; and a3) recovering copper phthalocyanine.Copper phthalocyanine, obtained by such processes using anthranilic acid produced or obtained by a biological process from a microorganism, in particular E. coli, may comprise a percentage of modern carbon equal to or greater than 80%, preferably equal to or greater than 87.5%, and even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640. Also, copper phthalocyanine, obtained by such processes using anthranilic acid produced or obtained by a biological process from a microorganism, in particular E. coli, may comprise a bio-based carbon content equal to or greater than 80%, preferably equal to or greater than 87.5%, and even more preferably equal to or greater than 99%.

[0068] An object of the invention therefore relates to copper phthalocyanine comprising a percentage of modern carbon equal to or greater than 80%, preferably equal to or greater than 87.5%, even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640.

[0069] An object of the invention also relates to copper phthalocyanine comprising a percentage of modern carbon equal to or greater than 80%, preferably equal to or greater than 87.5%, even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640, obtained by a process or method of preparation comprising or consisting of the following steps: a) the culture of a microorganism, in particular of the species E. coli, to produce anthranilic acid; a) the reaction of anthranilic acid with sodium nitrite and sulfuric acid in an aqueous solution, followed by the addition of a cyanide salt to obtain 2-cyanobenzoic acid; a2) the reaction of 2-cyanobenzoic acid with copper chloride, urea, and ammonium molybdate in a solvent; and a3) the recovery of copper phthalocyanine.

[0070] 2-Cyanobenzoic acid is used as a reaction intermediate in the process for preparing copper phthalocyanine described above. A further object of the invention therefore relates to a process or method for preparing 2-cyanobenzoic acid comprising or consisting of the following steps: a) reacting anthranilic acid with sodium nitrite and sulfuric acid in aqueous solution, followed by the addition of a cyanide salt, in particular a mixture of sodium cyanide and copper cyanide, preferably at a temperature of about 0 °C; and a') recovering 2-cyanobenzoic acid.

[0071] Another additional object of the invention relates to a process or method for preparing 2-cyanobenzoic acid comprising or consisting of the following steps: a) the culture of a microorganism as described in the present application to produce anthranilic acid; a) the reaction of anthranilic acid with sodium nitrite and sulfuric acid in aqueous solution, followed by the addition of a cyanide salt, in particular a mixture of sodium cyanide and copper cyanide, preferably at a temperature of about 0 °C; and a) the recovery of 2-cyanobenzoic acid.

[0072] 2-Cyanobenzoic acid, obtained by such a process using anthranilic acid produced or obtained by a biological process from a microorganism, in particular E. coli, may comprise a percentage of modern carbon equal to or greater than 70%, preferably equal to or greater than 80%, and even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640. Also, 2-Cyanobenzoic acid, obtained by such a process using anthranilic acid produced or obtained by a biological process from a microorganism, in particular E. coli, may comprise a bio-based carbon content equal to or greater than 70%, preferably equal to or greater than 80%, and even more preferably equal to or greater than 99%.

[0073] An object of the invention therefore also relates to 2-cyanobenzoic acid comprising a percentage of modern carbon equal to or greater than 70%, preferably equal to or greater than 80%, even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640.

[0074] An object of the invention also relates to 2-cyanobenzoic acid comprising a percentage of modern carbon equal to or greater than 70%, preferably equal to or greater than 80%, even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640, obtained by a process or method of preparation comprising or consisting of the following steps: a) the culture of a microorganism, in particular of the species E. coli, to produce anthranilic acid; a) the reaction of anthranilic acid with sodium nitrite and sulfuric acid in an aqueous solution, followed by the addition of a cyanide salt, in particular a mixture of sodium cyanide and copper cyanide, preferably at a temperature of about 0 °C; and a) the recovery of 2-cyanobenzoic acid.

[0075] According to one aspect of the invention, anthranilic acid is used in a process for preparing quinacridone. Preferably, anthranilic acid is used in a process for preparing quinacridone as described in this application.

[0076] More specifically, two anthranilic acid motifs are condensed onto benzoquinone, followed by a cyclization reaction, a reduction reaction, and a re-aromatization to provide quinacridone (PV19).

[0077] One object of the invention therefore relates to a process or method for preparing quinacridone comprising the following steps: b1) reacting anthranilic acid with benzoquinone to obtain 2,2'-((3,6-dioxocyclohexa-l,4-diene-l,4-diyl)bis(azanediyl))dibenzoic acid; b2) reacting 2,2'-((3,6-dioxocyclohexa-l,4-diene-l,4-diyl)bis(azanediyl))dibenzoic acid with phosphoric anhydride to obtain quinacridonequinone; b3) reacting quinacridonequinone with zinc to obtain 6,13-dihydroquinacridone; b4) reacting 6,13-dihydroquinacridone with sodium 3-nitrobenzenesulfonate; and b5) the recovery of quinacridone.

[0078] An object of the invention also relates to a process or method for preparing quinacridone consisting of the following steps: b1) reacting anthranilic acid with benzoquinone to obtain 2,2'-((3,6-dioxocyclohexa-l,4-dien-l,4-diyl)bis(azanediyl))dibenzoic acid; b2) reacting 2,2'-((3,6-dioxocyclohexa-l,4-dien-l,4-diyl)bis(azanediyl))dibenzoic acid with phosphoric anhydride to obtain quinacridonequinone; b3) reacting quinacridonequinone with zinc to obtain 6,13-dihydroquinacridone; b4) reacting 6,13-dihydroquinacridone with sodium 3-nitrobenzenesulfonate; and b5) the recovery of quinacridone.

[0079] Step 1b) comprises the condensation of two anthranilic acid moieties onto benzoquinone. In one particular embodiment, step 1b) comprises reacting anthranilic acid with benzoquinone in a solvent at a temperature between 50 and 100 °C for 12 to 24 hours. Preferably, at least two equivalents, in particular two equivalents of anthranilic acid, relative to benzoquinone are used. Preferably, the solvent is a polar solvent, in particular ethanol. Preferably, step 1b) is carried out at a temperature between 60 and 90 °C, and even more preferably at a temperature of about 80 °C. Preferably, step 1b) is carried out for 16 to 20 hours, and even more preferably for about 18 hours.

[0080] Step b2) comprises the cyclization of 2,2'-((3,6-dioxocyclohexa-l,4-dien-l,4-diyl)bis(azanediyl))dibenzoic acid to quinacridonequinone. In one particular embodiment, step b2) comprises reacting 2,2'-((3,6-dioxocyclohexa-l,4-dien-l,4-diyl)bis(azanediyl))dibenzoic acid in a mixture of trifluoroacetic acid and methanesulfonic acid with phosphoric anhydride at a temperature between 40 and 100 °C for 12 to 24 hours. Preferably, step b2) is carried out at a temperature between 50 and 90 °C, between 60 and 80 °C, and even more preferably at a temperature of about 70 °C. Preferably, step b2) is carried out for 16 to 24 hours, and even more preferably for about 20 hours.

[0081] Step b3) comprises the reduction of quinacridonequinone to 6,13-dihydroquinacridone. In one particular embodiment, step b3) comprises reacting quinacridone with trifluoroacetic acid and zinc at a temperature between 40 and 100 °C for 12 to 24 hours. Preferably, step b3) is carried out at a temperature between 50 and 90 °C, between 60 and 80 °C, and even more preferably at a temperature of about 70 °C. Preferably, step b3) is carried out for 16 to 24 hours, and even more preferably for about 20 hours.

[0082] Step b4) comprises the rearomatization of 6,13-dihydroquinacridone to quinacridone. In one particular embodiment, step b4) comprises reacting 6,13-dihydroquinacridone with sodium 3-nitrobenzenesulfonate in the presence of a solvent, in particular a mixture of water and ethylene glycol, and a base, in particular sodium hydroxide and pyridine. Preferably, step b4) is carried out at a temperature between 60 and 100 °C, between 70 and 90 °C, and even more preferably at a temperature of about 80 °C. Preferably, step b4) is carried out for 30 minutes to 4 hours, for 1 to 3 hours, and even more preferably for about 2 hours.

[0083] An object is therefore a process or method for preparing quinacridone comprising or consisting of the following steps: bl) reacting anthranilic acid (2 eq.) with benzoquinone (1 eq.) in a solvent, preferably ethanol, at a temperature between 50 and 100 °C, preferably about 80 °C, for 12 to 24 hours, preferably about 18 hours, to obtain 2,2'-((3,6-dioxocyclohexa-l,4-diene-l,4-diyl)bis(azanediyl))dibenzoic acid; b2) the reaction of 2,2'-((3,6-dioxocyclohexa-l,4-diene-l,4-diyl)bis(azanediyl))dibenzoic acid in a mixture of trifluoroacetic acid and methanesulfonic acid with phosphoric anhydride at a temperature between 40 and 100 °C, preferably about 70 °C, for 12 to 24 hours, preferably for 20 hours to obtain quinacridonequinone;b3) the reaction of quinacridonequinone with trifluoroacetic acid and zinc at a temperature between 40 and 100 °C, preferably about 70 °C, for 12 to 24 hours, preferably for 20 hours to obtain 6,13-dihydroquinacridone; b4) the reaction of 6,13-dihydroquinacridone with sodium 3-nitrobenzenesulfonate in the presence of a solvent, in particular a mixture of water and ethylene glycol, and a base, in particular sodium hydroxide and pyridine, at a temperature between 60 and 100 °C, preferably about 80 °C, for 30 minutes to 4 hours, preferably for about 2 hours; and b5) the recovery of quinacridone. In particular, anthranilic acid is produced or obtained by a biological process from a microorganism, in particular a bacterium, preferably of the species Escherichia Coli.;

[0084] A particular object of the invention is therefore a process or method for preparing quinacridone comprising or consisting of the following steps: b1) the culture of a microorganism as described in this application to produce anthranilic acid; and steps b1), b2), b3), b4) and b5) as described in this application.

[0085] A particular object of the invention is also a process or method for preparing quinacridone comprising or consisting of the following steps: b0) the culture of a microorganism as described in the present application to produce anthranilic acid; b1) the reaction of anthranilic acid (2 eq.) with benzoquinone (1 eq.) in a solvent, preferably ethanol at a temperature between 50 and 100 °C, preferably about 80 °C, for 12 to 24 hours, preferably about 18 hours, to obtain 2,2'-((3,6-dioxocyclohexa-l,4-diene-l,4-diyl)bis(azanediyl))dibenzoic acid;b2) the reaction of 2,2'-((3,6-dioxocyclohexa-l,4-diene-l,4-diyl)bis(azanediyl))dibenzoic acid in a mixture of trifluoroacetic acid and methanesulfonic acid with phosphoric anhydride at a temperature between 40 and 100 °C, preferably about 70 °C, for 12 to 24 hours, preferably for 20 hours to obtain quinacridonequinone; b3) the reaction of quinacridonequinone with trifluoroacetic acid and zinc at a temperature between 40 and 100 °C, preferably about 70 °C, for 12 to 24 hours, preferably for 20 hours to obtain 6,13-dihydroquinacridone;b4) the reaction of 6,13-dihydroquinacridone with sodium 3-nitrobenzenesulfonate in the presence of a solvent, in particular a mixture of water and ethylene glycol, and a base, in particular sodium hydroxide and pyridine, at a temperature between 60 and 100 °C, preferably about 80 °C, for 30 minutes to 4 hours, preferably about 2 hours;and b5) the recovery of quinacridone. Quinacridone, obtained by such processes using anthranilic acid produced or obtained by a biological process from a microorganism, in particular E. coli, may comprise a percentage of modern carbon equal to or greater than 60%, preferably equal to or greater than 70%, even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640. Also, quinacridone, obtained by such processes using anthranilic acid produced or obtained by a biological process from a microorganism, in particular E. coli, may comprise a bio-based carbon content equal to or greater than 60%, preferably equal to or greater than 70%, even more preferably equal to or greater than 99%.

[0086] An object of the invention therefore relates to quinacridone comprising a percentage of modern carbon equal to or greater than 60%, preferably equal to or greater than 70%, even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640.

[0087] An object of the invention also relates to quinacridone comprising a percentage of modern carbon equal to or greater than 60%, preferably equal to or greater than 70%, even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640 obtained by a process or method of preparation comprising or consisting of the following steps: b0) the culture of a microorganism, in particular of species E.E. coli, to produce anthranilic acid; b1) the reaction of anthranilic acid with benzoquinone to obtain 2,2'-((3,6-dioxocyclohexa-l,4-diene-l,4-diyl)bis(azanediyl))dibenzoic acid; b2) the reaction of 2,2'-((3,6-dioxocyclohexa-l,4-diene-l,4-diyl)bis(azanediyl))dibenzoic acid with phosphoric anhydride to obtain quinacridonequinone; b3) the reaction of quinacridonequinone with zinc to obtain 6,13-dihydroquinacridone; b4) the reaction of 6,13-dihydroquinacridone with sodium 3-nitrobenzenesulfonate; and b5) the recovery of quinacridone. According to one aspect of the invention, anthranilic acid is used in a process for preparing 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanametamide (PY74).Preferably, anthranilic acid is used in a process for preparing 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide as described in this application.

[0088] More specifically, two synthons obtained from anthranilic acid, and more specifically from o-anisidine, are convergently condensed to obtain 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide.

[0089] An object of the invention therefore relates to a process or method for preparing 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide comprising the following steps: c1) obtaining o-anisidine from anthranilic acid; c2) obtaining p-nitro-o-anisidine from o-anisidine; c3) obtaining N-(2-methoxyphenyl)-3-oxobutanamide from o-anisidine; c4) obtaining 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide by coupling p-nitro-o-anisidine with N-(2-methoxyphenyl)-3-oxobutanamide; and c5) the recovery of 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutaamide.

[0090] An object of the invention also relates to a process or method for preparing 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide consisting of the following steps: c1) obtaining o-anisidine from anthranilic acid; c2) obtaining p-nitro-o-anisidine from o-anisidine; c3) obtaining N-(2-methoxyphenyl)-3-oxobutanamide from o-anisidine; c4) obtaining 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide by coupling p-nitro-o-anisidine with N-(2-methoxyphenyl)-3-oxobutanamide;and c5) the recovery of 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutamid. Step c1) includes the obtaining of o-anisidine from anthranilic acid. According to a particular embodiment, step c1) includes the following steps: c1a) reacting anthranilic acid with sulfuric acid and a sodium nitrite solution at a temperature between 90 and 130 °C, preferably about 100 °C, for 5 to 60 minutes, preferably about 20 minutes, to obtain salicylic acid; clb) the reaction of salicylic acid with potassium carbonate and dimethyl sulfate at a temperature between 40 and 80 °C, preferably about 60 °C, for 12 to 24 hours, preferably about 17 hours, to obtain methyl 2-methoxybenzoate;c) the reaction of methyl 2-methoxybenzoate with hydroxylamine and potassium hydroxide to obtain N-hydroxy-2-methoxybenzamide; cd) the reaction of N-hydroxy-2-methoxybenzamide with potassium carbonate and acetic anhydride at a temperature between 70 and 110 °C, preferably about 90 °C, for 2 to 6 hours, preferably about 4 hours; and ce) the recovery of o-anisidine.

[0091] Step c2) includes obtaining p-nitro-o-anisidine from o-anisidine. According to a particular embodiment, step c2) includes the following steps: c2a) reacting o-anisidine with acetic acid at a temperature between 90 and 140 °C, preferably about 115 °C, for 12 to 20 hours, preferably about 17 hours, to obtain N-(2-methoxyphenyl)acetamide; c2b) reacting N-(2-methoxyphenyl)acetamide with acetic anhydride and nitric acid at a temperature between 20 and 40 °C to obtain N-(2-methoxy-4-nitrophenyl)acetamide; and c2c) the reaction of N-(2-methoxy-4-nitrophenyl)acetamide in a sodium hydroxide solution at a temperature between 70 and 110 °C, preferably about 90 °C, for 12 to 24 hours, preferably about 17 hours; and c2d) the recovery of p-nitro-o-anisidine.

[0092] Step c3) includes obtaining N-(2-methoxyphenyl)-3-oxobutanamide from o-anisidine. According to a particular embodiment, step c3) includes reacting o-anisidine with ethyl acetoacetate and pyridine at a temperature between 90 and 130 °C, preferably about 100 °C, for 12 to 20 hours, preferably about 16 hours.

[0093] Step c4) comprises obtaining 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide (PY74) by coupling p-nitro-o-anisidine obtained in step c2) with N-(2-methoxyphenyl)-3-oxobutanamide obtained in step c3). According to a particular embodiment, step c4) comprises reacting an aqueous solution of p-nitro-o-anisidine and sodium nitrite with an aqueous solution of N-(2-methoxyphenyl)-3-oxobutanamide at a temperature between 15 and 25 °C, preferably about 20 °C, for 1 to 6 hours, preferably about 3 hours.

[0094] An object is therefore a process or method for preparing 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutamid comprising or consisting of the following steps: cia) reacting anthranilic acid with sulfuric acid and a sodium nitrite solution at a temperature between 90 and 130 °C, preferably about 100 °C, for 5 to 60 minutes, preferably about 20 minutes, to obtain salicylic acid; cb) reacting salicylic acid with potassium carbonate and dimethyl sulfate at a temperature between 40 and 80 °C, preferably about 60 °C, for 12 to 24 hours, preferably about 17 hours, to obtain methyl 2-methoxybenzoate; clc) the reaction of methyl 2-methoxybenzoate with hydroxylamine and potassium hydroxide to obtain N-hydroxy-2-methoxybenzamide;c2a) the reaction of N-hydroxy-2-methoxybenzamide with potassium carbonate and acetic anhydride at a temperature between 70 and 110 °C, preferably about 90 °C, for 2 to 6 hours, preferably about 4 hours, to obtain o-anisidine; c2a) the reaction of o-anisidine with acetic acid at a temperature between 90 and 140 °C, preferably about 115 °C, for 12 to 20 hours, preferably about 17 hours, to obtain N-(2-methoxyphenyl)acetamide; c2b) the reaction of N-(2-methoxyphenyl)acetamide with acetic anhydride and nitric acid at a temperature between 20 and 40 °C to obtain N-(2-methoxy-4-nitrophenyl)acetamide;and c2c) the reaction of N-(2-methoxy-4-nitrophenyl)acetamide in a sodium hydroxide solution at a temperature between 70 and 110 °C, preferably about 90 °C, for 12 to 24 hours, preferably about 17 hours, to obtain p-nitro-o-anisidine; c3) the reaction of o-anisidine with ethyl acetoacetate and pyridine at a temperature between 90 and 130 °C, preferably about 100 °C, for 12 to 20 hours, preferably about 16 hours, to obtain N-(2-methoxyphenyl)-3-oxobutanamide; c4) the reaction of an aqueous solution of p-nitro-o-anisidine and sodium nitrite with an aqueous solution of N-(2-methoxyphenyl)-3-oxobutanamide at a temperature between 15 and 25 °C, preferably about 20 °C, for 1 to 6 hours, preferably about 3 hours; and c5) the recovery of 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide.

[0095] In particular, anthranilic acid is produced or obtained by a biological process from a microorganism, in particular a bacterium, preferably of the species Escherichia Coli.

[0096] A particular object of the invention is therefore a process or method for preparing 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanametamide comprising or consisting of the following steps: c0) the culture of a microorganism as described in this application to produce anthranilic acid; and steps c1), c2), c3), c4) and c5) or c1a), c1b), c1c), c1d), c2a), c2b), c2c), c3, c4), and c5) as described in this application.

[0097] A particular object of the invention is also a process or method for preparing 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutamid comprising or consisting of the following steps: c) the culture of a microorganism as described in this application to produce anthranilic acid; cia) the reaction of anthranilic acid with sulfuric acid and a sodium nitrite solution at a temperature between 90 and 130 °C, preferably about 100 °C, for 5 to 60 minutes, preferably about 20 minutes to obtain salicylic acid; clb) the reaction of salicylic acid with potassium carbonate and dimethyl sulfate at a temperature between 40 and 80 °C, preferably about 60 °C, for 12 to 24 hours, preferably about 17 hours, to obtain methyl 2-methoxybenzoate;c1c) the reaction of methyl 2-methoxybenzoate with hydroxylamine and potassium hydroxide to obtain N-hydroxy-2-methoxybenzamide; c1d) the reaction of N-hydroxy-2-methoxybenzamide with potassium carbonate and acetic anhydride at a temperature between 70 and 110 °C, preferably about 90 °C, for 2 to 6 hours, preferably about 4 hours, to obtain o-anisidine; c2a) the reaction of o-anisidine with acetic acid at a temperature between 90 and 140 °C, preferably about 115 °C, for 12 to 20 hours, preferably about 17 hours, to obtain N-(2-methoxyphenyl)acetamide; c2b) the reaction of N-(2-methoxyphenyl)acetamide with acetic anhydride and nitric acid at a temperature between 20 and 40 °C to obtain N-(2-methoxy-4-nitrophenyl)acetamide;and c2c) the reaction of N-(2-methoxy-4-nitrophenyl)acetamide in a sodium hydroxide solution at a temperature between 70 and 110 °C, preferably about 90 °C, for 12 to 24 hours, preferably about 17 hours, to obtain p-nitro-o-anisidine; c3) the reaction of o-anisidine with ethyl acetoacetate and pyridine at a temperature between 90 and 130 °C, preferably about 100 °C, for 12 to 20 hours, preferably about 16 hours, to obtain N-(2-methoxyphenyl)-3-oxobutanamide; c4) the reaction of an aqueous solution of p-nitro-o-anisidine and sodium nitrite with an aqueous solution of N-(2-methoxyphenyl)-3-oxobutanamide at a temperature between 15 and 25 °C, preferably about 20 °C, for 1 to 6 hours, preferably about 3 hours; and c5) the recovery of 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide.

[0098] 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutananamide, obtained by such processes using anthranilic acid produced or obtained by a biological process from a microorganism, in particular E. coli, may comprise a percentage of modern carbon equal to or greater than 60%, preferably equal to or greater than 66.5%, preferably equal to or greater than 77.5%, and even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640. Also, 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutananamide, obtained by such processes using anthranilic acid produced or obtained by a biological process from a microorganism, in particular E.E. coli, may include a bio-based carbon content equal to or greater than 60%, preferably equal to or greater than 70%, preferably equal to or greater than 77.5%, even more preferably equal to or greater than 99%.

[0099] An object of the invention relates to 2-[(2-Methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanametamide comprising a percentage of modern carbon equal to or greater than 60%, preferably equal to or greater than 66.5%, preferably equal to or greater than 77.5%, and even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640.

[0100] An object of the invention also relates to 2-[(2-Methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutamid comprising a percentage of modern carbon equal to or greater than 60%, preferably equal to or greater than 66.5%, preferably equal to or greater than 77.5%, and even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640 obtained by a process or method of preparation comprising or consisting of the following steps: c0) the culture of a microorganism, in particular of species E.Coli, to produce anthranilic acid; c1) obtaining o-anisidine from anthranilic acid; c2) obtaining p-nitro-o-anisidine from o-anisidine; c3) obtaining N-(2-methoxyphenyl)-3-oxobutanamide from o-anisidine; c4) obtaining 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide by coupling p-nitro-o-anisidine with N-(2-methoxyphenyl)-3-oxobutanamide; and c5) recovering 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide. o-Anisidine is used as a reaction intermediate in the process for preparing 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutamid described above.

[0101] An additional object of the invention therefore relates to a process or method for preparing o-anisidine comprising or consisting of the following steps: cia) reacting anthranilic acid with sulfuric acid and a sodium nitrite solution at a temperature between 90 and 130 °C, preferably about 100 °C, for 5 to 60 minutes, preferably about 20 minutes to obtain salicylic acid; clb) reacting salicylic acid with potassium carbonate and dimethyl sulfate at a temperature between 40 and 80 °C, preferably about 60 °C, for 12 to 24 hours, preferably about 17 hours, to obtain methyl 2-methoxybenzoate; clc) the reaction of methyl 2-methoxybenzoate with hydroxylamine and potassium hydroxide to obtain N-hydroxy-2-methoxybenzamide;cld) the reaction of N-hydroxy-2-methoxybenzamide with potassium carbonate and acetic anhydride at a temperature between 70 and 110 °C, preferably about 90 °C, for 2 to 6 hours, preferably about 4 hours, to obtain o-anisidine; and c') the recovery of o-anisidine.

[0102] Another additional object of the invention also relates to a process or method for preparing o-anisidine comprising or consisting of the following steps: c0) the culture of a microorganism as described in the present application to produce anthranilic acid; c1) the reaction of anthranilic acid with sulfuric acid and a sodium nitrite solution at a temperature between 90 and 130 °C, preferably about 100 °C, for 5 to 60 minutes, preferably about 20 minutes, to obtain salicylic acid; c1b) the reaction of salicylic acid with potassium carbonate and dimethyl sulfate at a temperature between 40 and 80 °C, preferably about 60 °C, for 12 to 24 hours, preferably about 17 hours, to obtain methyl 2-methoxybenzoate;c) the reaction of methyl 2-methoxybenzoate with hydroxylamine and potassium hydroxide to obtain N-hydroxy-2-methoxybenzamide; cld) the reaction of N-hydroxy-2-methoxybenzamide with potassium carbonate and acetic anhydride at a temperature between 70 and 110 °C, preferably about 90 °C, for 2 to 6 hours, preferably about 4 hours, to obtain o-anisidine; and c') the recovery of o-anisidine.

[0103] o-Anisidine, obtained by such a process using anthranilic acid produced or obtained by a biological process from a microorganism, in particular E. coli, may comprise a percentage of modern carbon equal to or greater than 80%, preferably equal to or greater than 85%, even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640. Also, o-Anisidine, obtained by such a process using anthranilic acid produced or obtained by a biological process from a microorganism, in particular E. coli, may comprise a bio-based carbon content equal to or greater than 80%, preferably equal to or greater than 85%, even more preferably equal to or greater than 99%.

[0104] An object of the invention therefore also relates to o-anisidine comprising a percentage of modern carbon equal to or greater than 80%, preferably equal to or greater than 85%, even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640.

[0105] An object of the invention also relates to o-anisidine comprising a percentage of modern carbon equal to or greater than 80%, preferably equal to or greater than 85%, even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640 obtained by a process or method of preparation comprising or consisting of the following steps: c) the culture of a microorganism, in particular of the species E. coli to produce anthranilic acid; c) the reaction of anthranilic acid with sulfuric acid and a sodium nitrite solution at a temperature between 90 and 130 °C, preferably about 100 °C, for 5 to 60 minutes, preferably about 20 minutes to obtain salicylic acid;clb) the reaction of salicylic acid with potassium carbonate and dimethyl sulfate at a temperature between 40 and 80 °C, preferably about 60 °C, for 12 to 24 hours, preferably about 17 hours, to obtain methyl 2-methoxybenzoate; cc) the reaction of methyl 2-methoxybenzoate with hydroxylamine and potassium hydroxide to obtain N-hydroxy-2-methoxybenzamide; cld) the reaction of N-hydroxy-2-methoxybenzamide with potassium carbonate and acetic anhydride at a temperature between 70 and 110 °C, preferably about 90 °C, for 2 to 6 hours, preferably about 4 hours, to obtain o-anisidine; and c') the recovery of o-anisidine.

[0106] According to one aspect of the invention, anthranilic acid is used in a process for preparing 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid (PY151). Preferably, anthranilic acid is used in a process for preparing 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid as described in this application.

[0107] More specifically, 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid is obtained from two anthranilic acid motifs with a convergent reaction sequence. A first motif provides the diazonium salt of anthranilic acid. A second motif provides 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one, via the intermediate l,3-dihydrobenzimidazol-2-one (benzimidazolone), which is then coupled with the diazonium salt of anthranilic acid to provide 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid (PY151).

[0108] One object of the invention therefore relates to a process or method for preparing 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid, comprising the following steps: d1) obtaining 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one from anthranilic acid; and d2) reacting 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one with the diazonium salt of anthranilic acid; and d3) recovering 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid.

[0109] One object of the invention therefore relates to a process or method for preparing 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid, consisting of the following steps: d1) obtaining 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one from anthranilic acid; and d2) reacting 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one with the diazonium salt of anthranilic acid; and d3) recovering 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid.

[0110] Step dl) includes obtaining 5-acetoacetamido-1,3-dihydrobenzimidazol-2-one from anthranilic acid. According to a particular embodiment, step dl) includes the following steps: dla) reacting anthranilic acid with sulfuric acid in a solvent under reflux for 12 to 20 hours, preferably about 16 hours, to obtain methyl anthranilate; dlb) reacting methyl anthranilate with bis(hydroxylammonium) sulfate and followed by the addition of a sodium sulfite solution to obtain hydroxamic anthranilic acid; dlc) the reaction of hydroxamic anthranilic acid with ethyl chloroformiate in a basic solution at a temperature between 10 and 35 °C, preferably about 20 °C, for 1 to 4 hours, preferably about two hours to obtain 1,3-dihydrobenzimidazol-2-one;did) the reaction of 1,3-dihydrobenzimidazol-2-one with sulfuric acid and nitric acid at a temperature between 0 and 15 °C, preferably about 5 °C to obtain 5-nitro-1,3-dihydrobenzimidazol-2-one; die) the reaction of 5-nitro-1,3-dihydrobenzimidazol-2-one with palladium on carbon and ammonium formate in a solvent for 30 minutes to 12 hours, preferably about 1 hour to obtain 5-amino-1,3-dihydrobenzimidazol-2-one; dlf) the reaction of 5-amino-1,3-dihydrobenzimidazol-2-one with 2,2,6-trimethyl-4H-1,3-dioxine-4-one in refluxing water for 30 minutes to 3 hours; and dig) the recovery of 5-acetoacetamido-l-3-dihydrobenzimidazol-2-one.;

[0111] According to a preferred method, step dla) is carried out with the reflux of methanol for 16 hours.

[0112] According to a preferred method, step dlb) is carried out under basic conditions. A sodium hydroxide solution may be used. Preferably, step dlb) is carried out for 12 to 36 hours, particularly for approximately 24 hours.

[0113] According to a preferred method, the dlc step is carried out using a sodium hydroxide solution. Preferably, the dlc step is carried out at a temperature of approximately 20 °C for approximately 2 hours.

[0114] According to a preferred method for step did), 1,3-dihydrobenzimidazol-2-one is added to a solution of sulfuric acid and nitric acid at a temperature of about 5 °C and this step did) is carried out for about 1 hour.

[0115] According to a preferred method, the die step is carried out in methanol at a temperature between 15 and 25 °C for approximately 1 hour.

[0116] According to a preferred mode, the dlf step) is carried out for 1 to 2 hours, preferably for about 1 hour and 30 minutes.

[0117] Step d2) includes reacting 5-acetoacetamido-1,3-dihydrobenzimidazol-2-one with the diazonium salt of anthranilic acid. In particular, the diazonium salt of anthranilic acid is obtained by reacting anthranilic acid with a sodium nitrite solution. According to a preferred method, step d2) includes reacting an aqueous solution of anthranilic acid and sodium nitrite with an aqueous solution of 5-acetoacetamido-1,3-dihydrobenzimidazol-2-one at a temperature between 15 and 25 °C, preferably about 20 °C, for 1 to 6 hours, preferably about 2 hours. An object is therefore a process or method for preparing 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid comprising or consisting of the following steps: dla) reacting anthranilic acid with sulfuric acid in a solvent under reflux for 12 to 20 hours,preferably about 16 hours, to obtain methyl anthranilate; dlb) the reaction of methyl anthranilate with bis(hydroxylammonium) sulfate and followed by the addition of a sodium sulfite solution to obtain hydroxamic anthranilic acid; dlc) the reaction of hydroxamic anthranilic acid with ethyl chloride oformiate in a basic solution at a temperature between 10 and 35 °C, preferably about 20 °C, for 1 to 4 hours, preferably about two hours to obtain 1,3-dihydrobenzimidazol-2-one; did) the reaction of 1,3-dihydrobenzimidazol-2-one with sulfuric acid and nitric acid at a temperature between 0 and 15 °C, preferably about 5 °C to obtain 5-nitro-1,3-dihydrobenzimidazol-2-one; die) the reaction of 5-nitro-1,3-dihydrobenzimidazol-2-one with palladium on carbon and ammonium formate in a solvent for 30 minutes to 12 hours,preferably for about 1 hour, to obtain 5-amino-l,3-dihydrobenzimidazol-2-one; d1); the reaction of 5-amino-l,3-dihydrobenzimidazol-2-one with 2,2,6-trimethyl-4H-l,3-dioxin-4-one in refluxing water for 30 minutes to 3 hours, to obtain 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one; d2) the reaction of an aqueous solution of anthranilic acid and sodium nitrite with an aqueous solution of 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one at a temperature between 15 and 25 °C, preferably about 20 °C, for 1 to 6 hours, preferably about 2 hours; and d3) the recovery of 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid.,

[0118] In particular, anthranilic acid is produced or obtained by a biological process from a microorganism, in particular a bacterium, preferably of the species Escherichia coli. A particular object of the invention is therefore a process or method for preparing 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid comprising or consisting of the following steps: d0) the culture of a microorganism as described in this application to produce anthranilic acid; and steps d1), d2), and d3), or d1a), d1a), d1b), d1b), d1b), d1b), d1b), d1f), d1f), d2), and d3),) as described in this application.

[0119] A particular object of the invention is also a process or method for preparing 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid comprising or consisting of the following steps: d0) the culture of a microorganism as described in the present application to produce anthranilic acid; d1a) the reaction of anthranilic acid with sulfuric acid in a solvent under reflux for 12 to 20 hours, preferably about 16 hours, to obtain methyl anthranilate; d1b) the reaction of methyl anthranilate with bis(hydroxylammonium) sulfate and followed by the addition of a sodium sulfite solution to obtain hydroxamic anthranilic acid;dlc) the reaction of hydroxamic anthranilic acid with ethyl chloroformiate in a basic solution at a temperature between 10 and 35 °C, preferably about 20 °C, for 1 to 4 hours, preferably about two hours to obtain 1,3-dihydrobenzimidazol-2-one; did) the reaction of 1,3-dihydrobenzimidazol-2-one with sulfuric acid and nitric acid at a temperature between 0 and 15 °C, preferably about 5 °C to obtain 5-nitro-1,3-dihydrobenzimidazol-2-one; die) the reaction of 5-nitro-l,3-dihydrobenzimidazol-2-one with palladium on carbon and ammonium formate in a solvent for 30 minutes to 12 hours, preferably for about 1 hour, to obtain 5-amino-l,3-dihydrobenzimidazol-2-one; dlf);the reaction of 5-amino-l,3-dihydrobenzimidazol-2-one with 2,2,6-trimethyl-4H-l,3-dioxine-4-one in refluxing water for 30 minutes to 3 hours, to obtain 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one; d2) the reaction of an aqueous solution of anthranilic acid and sodium nitrite with an aqueous solution of 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one at a temperature between 15 and 25 °C, preferably about 20 °C, for 1 to 6 hours, preferably about 2 hours; and d3) the recovery of 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid.;

[0120] 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid, obtained by such processes using anthranilic acid produced or obtained by a biological process from a microorganism, in particular E. coli, may comprise a percentage of modern carbon equal to or greater than 60%, preferably equal to or greater than 77.5%, and even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640. Also, 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid, obtained by such processes using anthranilic acid produced or obtained by a biological process from a microorganism, in particular E.Co / z, may include a bio-based carbon content equal to or greater than 60%, preferably equal to or greater than 77.5%, even more preferably equal to or greater than 99%.

[0121] An object of the invention relates to 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol- 5-yl)carbamoyl]propyl}diazenyl) benzoic acid comprising a percentage of modern carbon equal to or greater than 60%, preferably equal to or greater than 77.5%, and even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640.

[0122] An object of the invention also relates to 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid comprising a percentage of modern carbon equal to or greater than 60%, preferably equal to or greater than 77.5%, and even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640 obtained by a process or method of preparation comprising or consisting of the following steps: d0) the culture of a microorganism, in particular of species E.Coli, to produce anthranilic acid; d1) obtaining 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one from anthranilic acid; and d2) reacting 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one with the diazonium salt of anthranilic acid; and d3) recovering 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid.

[0123] 1,3-Dihydrobenzimidazol-2-one or benzimidazolone is used as a reaction intermediate in the process for preparing 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid described above.

[0124] An additional object of the invention therefore relates to a process or method for preparing 1,3-dihydrobenzimidazol-2-one comprising or consisting of the following steps: dla) reacting anthranilic acid with sulfuric acid in a refluxing solvent for 12 to 20 hours, preferably about 16 hours, to obtain methyl anthranilate; dlb) reacting methyl anthranilate with bis(hydroxylammonium) sulfate and followed by the addition of a sodium sulfite solution to obtain hydroxamic anthranilic acid; dlc) reacting hydroxamic anthranilic acid with ethyl chloride in a basic solution at a temperature between 10 and 35 °C, preferably about 20 °C, for 1 to 4 hours, preferably about two hours; and dl') the recovery of l,3-dihydrobenzimidazol-2-one.

[0125] Another additional object of the invention also relates to a process or method for preparing 1,3-dihydrobenzimidazol-2-one comprising or consisting of the following steps: d0) the culture of a microorganism as described in the present application to produce anthranilic acid; d1a) the reaction of anthranilic acid with sulfuric acid in a solvent under reflux for 12 to 20 hours, preferably about 16 hours, to obtain methyl anthranilate; d1b) the reaction of methyl anthranilate with bis(hydroxylammonium) sulfate and followed by the addition of a sodium sulfite solution to obtain hydroxamic anthranilic acid; dlc) the reaction of hydroxamic anthranilic acid with ethyl chloroformiate in a basic solution at a temperature between 10 and 35 °C, preferably about 20 °C, for 1 to 4 hours, preferably about two hours;and dl') the recovery of l,3-dihydrobenzimidazol-2-one.;

[0126] L,3-Dihydrobenzimidazol-2-one, obtained by such a process using anthranilic acid produced or obtained by a biological process from a microorganism, in particular E. coli, may comprise a percentage of modern carbon equal to or greater than 90%, preferably equal to or greater than 95%, even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640. Also, L,3-Dihydrobenzimidazol-2-one, obtained by such a process using anthranilic acid produced or obtained by a biological process from a microorganism, in particular E. coli, may comprise a bio-based carbon content equal to or greater than 90%, preferably equal to or greater than 95%, even more preferably equal to or greater than 99%.

[0127] An object of the invention relates to 1,3-Dihydrobenzimidazol-2-one comprising a percentage of modern carbon equal to or greater than 90%, preferably equal to or greater than 95%, and even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640.

[0128] An object of the invention also relates to 1,3-Dihydrobenzimidazol-2-one comprising a percentage of modern carbon equal to or greater than 90%, preferably equal to or greater than 95%, and even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640 obtained by a process or method of preparation comprising or consisting of the following steps: d0) the culture of a microorganism, in particular of species E.Coli, to produce anthranilic acid; dla) the reaction of anthranilic acid with sulfuric acid in a solvent under reflux for 12 to 20 hours, preferably about 16 hours, to obtain methyl anthranilate; dlb) the reaction of methyl anthranilate with bis(hydroxylammonium) sulfate and followed by the addition of a sodium sulfite solution to obtain hydroxamic anthranilic acid; dlc) the reaction of hydroxamic anthranilic acid with ethyl chloride oformiate in a basic solution at a temperature between 10 and 35 °C, preferably about 20 °C, for 1 to 4 hours, preferably about two hours; and dl') the recovery of 1,3-dihydrobenzimidazol-2-one.

[0129] The processes or methods for preparing the compounds of interest and their reaction intermediates described above all include a final step of recovering the compound of interest. It is understood that a person skilled in the art knows how to recover the compound of interest after a reaction step, thanks to their general knowledge as an organic chemist. These recovery steps may include one or more treatment steps of the reaction mixture and one or more isolation and / or purification steps. For example, isolation and purification steps include distillation, evaporation, concentration, filtration, and / or drying.

[0130] The invention will be better understood in light of the following examples, which are given purely for illustrative purposes and are not intended to limit the scope of the invention as defined by the attached claims.

[0131] EXAMPLES

[0132] Example 1. Process for preparing copper phthalocyanine (PB15:3)

[0133] 1. Industrial synthesis

[0134] Scheme 1A below illustrates the common industrial synthesis of copper phthalocyanine. There are two processes for the industrial production of copper phthalocyanine. The first method involves heating (T° > 200 °C) phthalic anhydride or a derivative of phthalic acid, urea, or a derivative of urea in the presence of a copper salt and possibly a catalyst. The second process involves heating (T° > 200 °C) phthalonitrile with a copper salt. Both approaches can be carried out with or without a solvent by adjusting the heating and reaction time.

[0135] AI diagram:

[0136] Today, the synthesis of phthalonitrile is derived from that of phthalimides. The oxidation of naphthalene in the gas phase in the presence of vanadium catalysts generates phthalic anhydride. The latter can be hydrolyzed to phthalic acid, which can in turn be converted to phthalimide, which is then dehydrated to phthalonitrile (Scheme IB).

[0137] Diagram IB:

[0138] 2. Synthesis according to the invention

[0139] The process for synthesizing copper phthalocyanine from anthranilic acid according to the invention is illustrated by the IC diagram below. It comprises the substitution of the amine function of anthranilic acid with a cyano group via a Sandmeyer reaction, followed by tetrameric cyclization to provide copper phthalocyanine (PB 15:3). IC diagram:

[0140] A solution of sodium nitrite (1.20 eq, 604 mg, 8.75 mmol) in water (5 mL, 5 vol) was added dropwise at 0 °C to a mixture of anthranilic acid, possibly bio-based (1 eq, 1.00 g, 7.29 mmol), in sulfuric acid (0.6 eq, 0.23 mL, 4.38 mmol) and water (20 mL). The reaction was stirred for 30 min at 0 °C. The excess NaNCl was neutralized with sulfamic acid (0.3 eq, 212 mg, 2.19 mmol), and the mixture was then acidified with a saturated Na₂CO₃ solution to pH 7–8 before being added to a mixture of copper(I) cyanide (1 eq, 653 mg, 7.29 mmol) and sodium cyanide (1 eq, 357 mg, 7.29 mmol) in a 20 mL, 20-vol Na₂CO₃ / NaHC₃ buffer solution. The reaction was then stirred at room temperature for 1 h. Next, 30 mL of a 10% Na₂S₂O₃ solution (1.5 eq) was added, and the reaction was acidified with H₂SO₄ until pH 2 was reached.The organic phase was extracted with ethyl acetate, washed with water and brine, dried over MgSCU and concentrated under reduced pressure to give 900 mg of 2-cyanobenzoic acid with a yield of 67% and a purity of 80%. H NMR (400 MHz, DMSO) δ (ppm) 8.13 - 8.07 (m, 1H), 7.99 - 7.95 (m, 1H), 7.84 - 7.76 (m, 2H).

[0141] 2-Cyanobenzoic acid (400 mg, 2.72 mmol), copper chloride (81 mg, 0.815 mmol, 0.3 eq.), urea (653 mg, 10.87 mmol, 4 eq.) and ammonium molybdate (27 mg, 0.136 mmol, 0.05 eq.) were dissolved in anisole (6 mL, 15 vol) and heated at 155 °C for 16 h. The reaction was then cooled to room temperature and the blue precipitate was filtered and washed with water, a 5% H2SO4 solution (50 mL) and then water until a neutral pH was obtained. The mixture was oven-dried for 24 h to provide copper phthalocyanine in the form of a blue powder (355 mg, gross yield of 90%).

[0142] Compared to commonly used industrial synthesis methods, the process for synthesizing copper phthalocyanine from anthranilic acid according to the invention is industrially attractive because it considerably reduces the number of steps: one to obtain 2-cyanobenzoic acid and one to obtain copper phthalocyanine. Example 2. Process for preparing quinacridone (PV19)

[0143] 1. Industrial synthesis

[0144] Scheme 2A below illustrates the common industrial synthesis of quinacridone. The process developed in 1955 by DuPont (Hunger, K.; Herbst, W. Pigments, Organic. In Ullmann's Encyclopedia of Industrial Chemistry; John Wiley & Sons, Ltd, 2000) involves reacting the succinosuccinate ester, obtained from the corresponding succinate, with an aromatic amine (aniline, p- or m-toluidine, 4- or 3-chloroaniline) to form the dihydroterephthalic diester. The latter can be directly converted to dihydroquinacridone by thermal intramolecular cyclization in the same reaction medium at 250 °C. The dihydroquinacridone is then oxidized in aqueous solution to form quinacridone.

[0145] Diagram 2A:

[0146] 2. Synthesis according to the invention

[0147] The process for synthesizing quinacridone from anthranilic acid according to the invention is illustrated by Scheme 2B below. It comprises an addition step [1,4] of anthranilic acid to benzoquinone followed by a cyclization step, a reduction step, and a re-aromatization step to provide quinacridone (PV19).

[0148] Diagram 2B:

[0149] Benzoquinone (35.5 g, 328.13 mmol, 1.8 eq.) was added to a solution of anthranilic acid (50 g, 364.59 mmol, 2 eq.), possibly bio-based, in ethanol (250 mL, 5 vol.). The reaction mixture was stirred at 80 °C for 18 h. It was then filtered and washed with ethanol. The filtered solid was oven-dried at 70 °C to give 2,2'-((3,6-dioxocyclohexa-l,4-dien-l,4-diyl)bis(azanediyl))dibenzoic acid (37.5 g, yield 54%, purity 89%) as a reddish-brown powder. 'H NMR (400 MHz, DMSO-dô) ô (ppm): 10.74 (s, 2H), 8.03 (dd, J = 8.1, 1.7 Hz, 2H), 7.74 - 7.60 (m, 4H), 7.27 (ddd, J = 8.1, 6.5, 1.7 Hz, 2H), 6.25 (s, 2H).

[0150] 2,2'-((3,6-dioxocyclohexa-1,4-diene-1,4-diyl)bis(azanediyl))dibenzoic acid (3.0 g, 7.93 mmol, 1 eq.) was dissolved in a mixture of trifluoroacetic acid (27 mL, 9 vol.) and methanesulfonic acid (3 mL, 1 vol.). Phosphoric anhydride (3.04 g, 21.41 mmol, 2.7 eq.) was then added to the reaction mixture. The mixture was heated to 70 °C and maintained at this temperature for 20 h. The mixture was cooled to room temperature and poured into water. The resulting precipitate was filtered and then dried at 70 °C in an oven to obtain quinacridonequinone (5.025 g, quantitative yield, 56% purity) as a light brown solid. 'H NMR (400 MHz, D2O / D2SO4) ô (ppm): 3.03 (d, J = 8.3 Hz, 2H), 2.69 - 2.64 (m, 4H), 2.39 (ddd, J = 8.3, 5.4, 2.7 Hz, 2H).

[0151] Quinacridonequinone (6.741 g, 17.82 mmol, 1 eq.) was dissolved in trifluoroacetic acid (68 mL, 10 vol.) before the addition of zinc powder (6.058 g, 92.65 mmol, 4.9 eq.). The reaction mixture was stirred at 70 °C for 20 h. The reaction mixture was concentrated under vacuum to 2 volumes and then poured onto cold water. The precipitate formed was filtered and oven-dried at 70 °C to give 6,13-dihydroquinacridone (10.446 g, quantitative yield, 59% purity) as a brown solid. 'H NMR (400 MHz, D2O / D2SO4) ô (ppm): 2.51 (d, J = 8.6 Hz, 2H), 2.27 (t, J = 7.9 Hz, 2H), 2.16 (d, J = 8.6 Hz, 2H), 2.05 (t, J = 7.9 Hz, 2H), 1.5 (s, 4H).

[0152] In a 250 mL single-necked round-bottom flask equipped with a water-cooled condenser, 6,13-dihydroquinacridone (3.40 g, 6.17 mmol, 1.0 eq) was introduced, along with ethylene glycol (26 mL, 7.6 vol) and water (22 mL, 6.5 vol). Sodium 3-nitrobenzenesulfonate (3.41 g, 15.1 mmol, 1.4 eq), pyridine (20 mL, 249 mmol, 23 eq), and sodium hydroxide (6.92 g, 173 mmol, 16 eq) were then added. The reaction mixture was stirred at 80 °C for 2 h. The mixture was then cooled to room temperature. Water was added to the mixture. A pink precipitate was formed, which was filtered and rinsed three times with hot water (80 °C), then with ethanol. The solid was oven-dried at 70 °C, yielding quinacridone (2.70 g, 72% yield, 90% purity). ¹H NMR (400 MHz, D₂O / D₂SO₄) δ (ppm): 3.44 (s, 2H), 2.51 (d, J = 8.9 Hz, 2H), 2.26 (t, J = 7.9 Hz, 2H), 2.04 (d, J = 8.8 Hz, 2H), 1.81 (t, J = 8.0 Hz, 2H).Compared to commonly used industrial synthesis methods, the process for synthesizing quinacridone from anthranilic acid according to the invention is industrially attractive because it is carried out at temperatures and pressures more suitable for industrial scale (< 200 °C). Furthermore, it uses distillable acids, facilitating purification and recycling.

[0153] Example 3. Process for preparing 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutaamide (PY74)

[0154] 1. Industrial synthesis

[0155] The industrial synthetic route of 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide (PY74) involves azo coupling between the diazonium salt of 5-nitro-2-aminoanisole and o-acetoacetanisidide by heating the mixture in a basic medium (EP 1,424,370 and US 4,457,783). This synthetic route yields PY74 with a variety of toxic or carcinogenic aromatic amine impurities that are difficult to remove and uses anisidine as a starting material.

[0156] The main industrial route for anisidine production involves the reduction of an o-nitroanisole derivative to produce ortho-anisidine (CN103073436). The o-anisidine obtained via this route contains byproducts that are difficult to separate. Furthermore, a considerable amount of wastewater is generated, and this wastewater is difficult to treat.

[0157] 2. Synthesis according to the invention

[0158] The process for synthesizing 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutamidine from anthranilic acid according to the invention is illustrated by Scheme 3A below. The o-anisidine obtained is converted, on the one hand, into p-nitro-o-anisidine and, on the other hand, into aromatic acetoacetamide, which react via an azo coupling reaction. Scheme 3A:

[0159] The process for synthesizing o-anisidine from anthranilic acid according to the invention is illustrated in Scheme 3B below. It yields ortho-anisidine via a Sandmeyer-type step to obtain salicylic acid, followed by O-alkylation before conversion to N-hydroxyamide. Finally, 2-hydroxymethoxybenzamide rearranges to o-anisidine under basic conditions in the presence of acetic anhydride.

[0160] Diagram 3B:

[0161] Ice (192 g), sulfuric acid (58 mL, 1.09 mol, 30 eq.), and anthranilic acid (5 g, 36.5 mmol), optionally bio-based, were added to a single-necked flask equipped with a magnetic stir bar. The reaction mixture was stirred for 10 min. CPME (261 mL) was then added, followed by an aqueous solution (101 mL) of sodium nitrite (2.79 g, 40.2 mmol, 1.1 eq.) dropwise. After the addition, the mixture was heated to 110 °C and maintained at this temperature for 20 min. The reaction was cooled to room temperature and then extracted with ethyl acetate. The organic phase was dried with magnesium sulfate, then filtered and concentrated under vacuum to yield salicylic acid. (3.64 g, yield 73%). NMR 'H (400 MHz, DMSO) ô (ppm): 11.25 (s, 1H), 7.79 (dd, J = 7.9, 1.8 Hz, 1H), 7.51 (ddd, J = 8.3, 7.2, 1.8 Hz, 1H), 6.95 (dd, J = 8.2, 1.1 Hz, 1H), 6.93 - 6.89 (m, 1H). MS (EI) m / z 138.

[0162] Salicylic acid (3.6 g, 0.026 mol) and potassium carbonate (10.5 g, 0.076 mol, 2.91 eq.) were added to a single-necked flask fitted with a magnetic stir bar. Acetone (15 mL) and dimethyl sulfate (7.2 mL, 0.076 mol, 2.91 eq.) were then added to the reaction mixture. The mixture was stirred at 60 °C for 17 h. After cooling to room temperature, water (51 mL) was added to the mixture, which was stirred for another h. It was then extracted with ethyl acetate. The organic phase was washed with brine solution and then dried with magnesium sulfate. It was filtered and concentrated under vacuum to give methyl 2-methoxybenzoate (4 g, 93% yield). 'H NMR (400 MHz, DMSO) δ (ppm): 7.63 (dd, J = 7.7, 1.9 Hz, 1H), 7.53 (ddd, J = 8.4, 7.3, 1.8 Hz, 1H), 7.14 (dd, J = 8.5, 1.0 Hz, 1H), 7.01 (td, J = 7.5, 1.0 Hz, 1H), 3.81 (s, 3H), 3.78 (s, 3H). MS (El) m / z 166.

[0163] Hydroxylamine hydrochloride (16.68 g, 0.24 mol, 10 eq.), potassium hydroxide (26.93 g, 0.48 mol, 20 eq.), and methanol (100 mL) were added to a single-necked flask equipped with a magnetic stir bar at 0 °C. Gas escape was observed. A methanolic solution (60 mL) of methyl 2-methoxybenzoate (3.99 g, 0.024 mol) was added to the system. The mixture was stirred at room temperature for 1 h. After complete conversion, a 10% w / w citric acid solution (260 mL) was added. The mixture was stirred for another 10 min before being extracted with dichloromethane (6 x 150 mL). The organic phase was dried with magnesium sulfate and the solvent was evaporated under vacuum to give N-hydroxy-2-methoxybenzamide (3.72 g, quantitative yield, purity 93%). ¹H NMR (400 MHz, DMSO) β (ppm): 10.62 (s, 1H), 9.08 (s, 1H), 7.56 (dd, J = 7.6, 1.8 Hz, 1H), 7.44 (ddd, J = 8.3, 7.3, 1.8 Hz, 1H), 7.09 (dd, J = 8.4, 1.0 Hz, 1H), 7.01 (td, J = 7.4, 1.0 Hz, 1H), 3.83 (s, 3H).MS (El) m / z 167.

[0164] N-Hydroxy-2-Methoxybenzamide (8.6 g, 52.2 mmol) was added to a single-necked flask equipped with a magnetic stir bar. Potassium carbonate (7.1 g, 51.2 mmol, 1 eq) was then added. The glassware was rendered inert with argon before the addition of DMSO (118 mL) and acetic anhydride (241 pL, 2.6 mmol, 0.05 eq). The mixture was stirred at 90 °C for 4 h. After returning to room temperature, a 2 M hydrochloric acid solution (260 mL) was added. The mixture was stirred for 10 min. A 2 M sodium hydroxide solution (260 mL) was then added. The mixture was extracted with diethyl ether (9 x 100 mL). The organic phase was washed with a 10% w / w lithium chloride solution (5 x 100 mL) and brine (5 x 100 mL). It was then dried with magnesium sulfate, filtered, and concentrated under vacuum to give o-anisidine (4.7 g, 79% yield, 98% purity).'H NMR (400 MHz, DMSO-dô) ô (ppm): = 6.77 (dd, J=7.9, 1.3, 1H), 6.67 (ddd, J=8.3, 7.0, 1.3, 1H), 6.63 (dd, J=7.7, 2.0, 1H), 6.52 (ddd, J=8.0, 7.0, 2.0, 1H), 4.65 (s, 2H), 3.74 (s, 3H). MS (El) m / z 123.

[0165] o-Anisidine (0.183 g, 1.49 mmol) and acetic acid (0.231 mL, 4.03 mmol, 2.7 eq.) were added to a microwave reactor. The mixture was stirred at 115 °C for 17 h. The mixture was evaporated under vacuum to give N-(2-methoxyphenyl)acetamide (0.215 g, yield 87%, purity 74% by GC-MS). NMR 'H (400 MHz, DMSO-d6) ô (ppm): 9.11 (s, 1H), 7.95 - 7.88 (m, 1H), 7.10 - 7.01 (m, 2H), 6.88 (ddd, J = 8.6, 6.9, 1.9 Hz, 1H), 3.82 (s, 3H), 2.08 (s, 3H). MS (El) m / z 165.

[0166] N-(2-Methoxyphenyl)acetamide (0.215 g, 1.30 mmol) and acetic anhydride (0.357 mL, 3.77 mmol, 2.9 eq.) were dissolved in dichloromethane (1.1 mL, 5 vol.) and the mixture was stirred for 30 min at room temperature. Nitric acid 66% (0.059 mL, 1.30 mmol, 1 eq.) was added before stirring the mixture at room temperature for 17 h. Nitric acid 66% (0.059 mL, 1.30 mmol, 1 eq.) was added again, and the mixture was stirred at 30 °C for another 17 h. The mixture was then transferred to water (5 mL) and extracted with dichloromethane (3 x 5 mL). The organic phase was dried with sodium sulfate, filtered, and then evaporated under vacuum to give N-(2-methoxy-4-nitrophenyl)acetamide (0.157 g, 0.75 mmol, yield 57%, GC-MS purity 77%). ¹H NMR (CDCh) (ppm): 8.58 (d, J = 9.0 Hz, 1H), 7.97 (large s, 1H, NH), 7.92 (dd, J = 9.0 Hz, 2.4 Hz, 1H), 7.75 (d, J = 2.4 Hz, 1H), 4.01 (s, 3H), 2.27 (s, 3H). MS (El) m / z 210.

[0167] N-(2-Methoxy-4-nitrophenyl)acetamide (916 mg, 4.36 mmol, 1 eq.) was introduced with 2 M sodium hydroxide solution (20.1 mL, 22 vol) into a 50 mL single-necked flask fitted with a magnetic stir bar. The mixture was stirred for 17 h at 90 °C. The mixture was heterogeneous at the beginning and end of the reaction. After cooling to room temperature, the mixture was acidified to pH 1 with concentrated sulfuric acid. The aqueous solution was then extracted with ethyl acetate. The organic phase was dried with magnesium sulfate and concentrated under vacuum to give 2-Methoxy-4-nitroaniline (683 mg, 93% yield) as an orange solid. 'H NMR (400 MHz, CDCh) ô (ppm): 7.74 (dd, J = 8.7, 2.4 Hz, 1H), 7.60 (d, J = 2.4 Hz, 1H), 6.57 (d, J = 8.7 Hz, 1H), 3.87 (s, 3H).

[0168] o-Anisidine (1.22 mL, 11.0 mmol, 1 eq.), ethyl acetoacetate (1.39 mL, 11.0 mmol, 1 eq.), and toluene (20 mL, 14.8 vol.) were introduced into a 50 mL flask equipped with a magnetic stir bar. Pyridine was then added (50 pL, 0.56 mmol, 5.6 mol%). The mixture was stirred for 16 h at 110 °C. It was then concentrated under vacuum to give N-(2-methoxyphenyl)-3-oxobutanametamide as a yellow oil (2.102 g, yield 75%, purity 81%). 'H NMR (400 MHz, CDCh) ô (ppm): 9.23 (s, 1H), 8.32 (dd, J = 8.0, 1.6 Hz, 1H), 7.06 (td, J = 7.8, 1.7 Hz, 1H), 6.96 (d, J = 8.2 Hz, 1H), 6.89 (dd, J = 8.1, 1.4 Hz, 1H), 3.92 (s, 3H), 3.60 (s, 2H), 2.33 (s, 3H). MS (El) m / z 207. 2-Methoxy-4-Nitroaniline (202 mg, 1.20 mmol, 1 eq.) was added to a mixture of water (1.7 mL, 8.4 vol.) and 35% hydrochloric acid (308 pL, 10.1 mmol, 8.3 eq.). The solution was cooled to 0°C. Diazotization was performed by adding sodium nitrite (87 mg, 1.26 mmol, 1.05 eq.).In a separate reactor, 2-methoxyacetoacetoanilide (258 mg, 1.24 mmol, 1.03 eq.) was dissolved in 6.6 mL of 0.2 M aqueous sodium hydroxide solution. After the addition of 46 qL (0.18 vol.) of 90% acetic acid and 244 mg (2.97 mmol, 2.5 eq.), the diazo solution was poured into acetate buffer for 3 h at 20 °C. After complete conversion of the coupling, the aqueous suspension was heated to 85 °C for 45 min. The reaction mixture was then filtered, washed with water, and oven-dried at 70 °C to give PY74 as a yellow solid (300 mg, 65% yield). 'H NMR (500 MHz, CDCh) ô (ppm): 14.74 (bs, 1H), 11.65 (bs, 1H), 8.41 (dd, 1H), 7.98 (dd, 1H), 7.86 (d, 1H), 7.78 (d, 1H), 7.13 (dt, 1H), 6.99 (dt, 1H), 6.98 (dd, 1H), 4.09 (s, 3H), 3.97 (s, 3H), 2.61 (s, 3H).

[0169] Compared to the commonly used industrial synthesis, the process for synthesizing PY74 from anthranilic acid is industrially attractive because it includes a convergent synthetic route with a common synthon o-anisidine, reaction conditions with temperatures < 110 °C, and assured regioselectivity which eliminates the need for regioisomer separation.

[0170] Example 4. Process for the preparation of 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid

[0171] 1. Industrial synthesis

[0172] The synthetic route for 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid (PY151) is commonly obtained by azo coupling of the diazonium salt derived from anthranilic acid with 5-N-acetoacetylaminobenzimidazolone (Hunger, K.; Herbst, W. Pigments, Organic. In Ullmann's Encyclopedia of Industrial Chemistry; John Wiley & Sons, Ltd, 2000.). The latter is itself obtained by reacting the acetoacetic ester or diketene with 5-aminobenzimidazolone. Current industrial synthesis routes for benzimidazolone rely on the use of urea or phosgene on orthophenylenediamine under drastic pressure and temperature conditions (CN 117447405). They use organic solvents and harmful reagents (phosgene), and generate a large amount of corrosive waste and reaction by-products (HCl).Finally, yields are often low and are obtained through energy-intensive processes.

[0173] 2. Synthesis according to T invention

[0174] The process for synthesizing 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid from anthranilic acid according to the invention is illustrated by Scheme 4A below. The two aromatic rings of PY151 thus originate from the functionalization of anthranilic acid as a diazonium salt on the one hand and as 1,3-dihydrobenzimidazol-2-one on the other.

[0175] Diagram 4A:

[0176] In an IL flask, anthranilic acid (10 g, 68.5 mmol, purity: 93%), possibly bio-based, was dissolved in anhydrous methanol (500 mL). Then, 95% H₂SO₄ (17 mL, 298 mmol) was added dropwise. After the acid addition, the mixture was heated under reflux for 16 hours. The reaction was neutralized with a saturated NaHCl solution (400 mL), followed by extraction with EtOAc (3 x 200 mL). The organic phase was washed with a saturated NaHCl solution (100 mL), brine (250 mL), then dried over MgSCU, filtered, and concentrated under vacuum to give methyl anthranilate in liquid form (9.95 g, purity: >95%, yield: 97%). 'H NMR (400 MHz, DMSO) ô 7.69 (dd, J = 8.1, 1.6 Hz, 1H), 7.24 (ddd, J = 8.5, 7.0, 1.6 Hz, 1H), 6.76 (dd, J = 8.5, 1.2 Hz, 1H), 6.63 (s, 2H), 6.52 (ddd, J = 8.1, 7.0, 1.2 Hz, 1H), 3.78 (s, 3H).In a 100 mL round-bottom flask, bis(hydroxylammonium) sulfate (10.86 g, 66.2 mmol) was dissolved in 25 mL of deionized water. To this solution, a solution of sodium hydroxide (7.94 g, 198 mmol) in 25 mL of deionized water was added. After 10 minutes, a solution of sodium sulfite (1.25 g, 9.92 mmol) in 5 mL of deionized water was added dropwise to the mixture, followed by methyl anthranilate (8.6 mL, 66.2 mmol). The heterogeneous solution was stirred for 24 hours. The reaction was acidified with glacial acetic acid (4.0 mL), the solid formed was filtered and dried to give hydroxamic anthranilic acid (9.30 g, purity: 73%, yield: 67%) as a white crystalline solid. 'H NMR (400 MHz, DMSO) ô 10.85 (bs, 1H), 8.90 (bs, 1H), 7.31 (dd, J = 7.9, 1.5 Hz, 1H), 7.17 - 7.04 (m, 1H), 6.69 (d, J = 8.2 Hz, 1H), 6.48 (t, J = 7.5 Hz, 1H), 6.22 (s, 2H).

[0177] In a 100 mL round-bottom flask, sodium hydroxide (1.21 g, 30.2 mmol) was dissolved in deionized water (16 mL). Hydroxamic anthranilic acid (2.00 g, 12.1 mmol) was then added in a single portion at 20 °C. After 5 minutes, ethyl chloride oformiate (1.4 mL, 14.5 mmol) was added dropwise to the mixture. The mixture was stirred at the same temperature for 2 hours. The resulting solid was filtered, washed with water, and oven-dried at 70 °C for 30 minutes to give 1,3-dihydrobenzimidazol-2-one (2.33 g, purity: 59%, yield: 85%) as a white solid. 'H NMR (400 MHz, DMSO) δ 10.57 (s, 2H), 6.91 (s, 4H).

[0178] In a 100 mL three-necked flask containing 22 mL of 95% H₂SO₄ at 5 °C, deionized water (7 mL) was added using an ice bath, followed by 1.0 mL of 90% nitric acid. Once the reaction had stabilized at 5 °C, 2.7 g (20 mmol) of 1,3-dihydrobenzimidazol-2-one was added in portions over a 10-minute period while maintaining the temperature below 10 °C. The mixture was stirred for one hour. The mixture was poured onto 100 mL of crushed ice, the flask was washed three times with 20 mL of deionized water, and then filtered. The solid obtained was dried at 55 °C for 20 hours to give 5-nitro-1,3-dihydrobenzimidazol-2-one (3.30 g, purity: 98%, yield: 90%) in the form of a beige solid. 'H NMR (400 MHz, DMSO) ô 11.29 (bs, 2H), 7.94 (dd, J = 8.6, 2.3 Hz, 1H), 7.71 (d, J = 2.3 Hz, 1H), 7.10 (d, J = 8.6 Hz, 1H).

[0179] In a 100 mL flask containing a suspension of 5-nitro-1,3-dihydrobenzimidazol-2-one (900 mg, 5.00 mmol) in anhydrous methanol (10 mL), 10% palladium on activated carbon (266 mg, 0.25 mmol) was added. Ammonium formate (1.58 g, 25.0 mmol) was then added per portion. The reaction was stirred at room temperature for 1 hour. The solution was filtered through Celite® and washed with methanol. The resulting solution was concentrated under vacuum to obtain a brown solid. The product was triturated in 96% ethanol and filtered to give 5-amino-1,3-dihydrobenzimidazol-2-one (291 mg, yield: 39%) as a pink solid. *HNMR (400 MHz, DMSO) ô 10.17 (s, 1H), 10.01 (s, 1H), 6.56 (d, J = 8.1 Hz, 1H), 6.23 (d, J = 2.1 Hz, 1H), 6.16 (dd, J = 8.1, 2.1 Hz, 1H), 4.62 (s, 2H).

[0180] In a 50 mL round-bottom flask containing a solution of 5-amino-1,3-dihydrobenzimidazol-2-one (746 mg, 5.0 mmol) in deionized water (15 mL) heated under reflux (105 °C), 2,2,6-trimethyl-4H-1,3-dioxine-4-one (1.06 mL, 8.0 mmol) was added. The solution was stirred under reflux for 1.5 hours. After the reaction mixture had cooled to room temperature, the solid was filtered and washed with water (3 x 5 mL) and dried at 70 °C for 16 hours to give 5-acetoacetamido-1,3-dihydrobenzimidazol-2-one (1.01 g, yield: 85%) as a light brown solid. Ketone / enol balance (9 / 1): *H NMR (400 MHz, DMSO) ô 13.82 (s, 0.1H), 10.54 (s, 1H), 10.49 (s, 1H), 9.93 (s, 0.9H), 9.77 (s, 0.1H), 7.44 (d, J = 2.1 Hz, 0.9H), 7.40 (d, J = 1.8 Hz, 0.lH), 6.96 (dd, J = 8.3, 2.0 Hz, 1H), 6.83 (d, J = 8.3 Hz, 1H), 5.14 (s, 0.lH), 3.50 (s, 1.8H), 2.20 (s, 2.7H), 1.90 (s, 0.3H).

[0181] In a 50 mL round-bottom flask, anthranilic acid (1.00 g, 7.29 mmol), possibly bio-based, deionized water (13.3 mL), and a 5 M HCl solution (3.3 mL, 16.7 mmol) were introduced. The mixture was stirred at room temperature until all the solids were dissolved. The reaction was then cooled to 0 °C, and a NaNCh solution (533 mg, 7.73 mmol) in water (1.33 mL) was added dropwise. The solution was stirred at the same temperature for 30 minutes. Finally, a urea solution (26 mg, 0.438 mmol) in deionized water (1 mL) was added to destroy the excess nitrite. In parallel, in a 100 mL flask, sodium hydroxide (917 mg, 22.9 mmol) was introduced into deionized water (16.7 mL), followed by 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one (1.75 g, 7.50 mmol).In a 250 mL round-bottom flask, 5 M sodium hydroxide (5.0 mL, 25.0 mmol) and water (33.3 mL) were introduced, followed by glacial acetic acid (2.5 mL, 43.7 mmol). To this buffered mixture, 5-acetoacetamido-1,3-dihydrobenzimidazol-2-one solution was added dropwise to obtain a white suspension. After this addition, the reaction was stirred for 10 minutes, and then cold diazonium anthranilate solution was added dropwise. The reaction was stirred for 2 hours at room temperature. The solid obtained was filtered, washed with water (3 x 40 mL) and vacuum-dried to give 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid (2.67 g, purity: >95%, yield: 91%) as a yellow-orange solid. 'H NMR (400 MHz, DMSO) ô 14.97 (bs, 1H), 13.55 (bs, 1H), 10.99 (s, 1H), 10.67 (s, 1H), 10.61 (s, 1H), 7.98 (dd, J = 7.9, 1.6 Hz, 1H), 7.95 (d, J = 8.3 Hz, 1H), 7.68 (t, J = 8.0 Hz, 1H), 7.60 (d, J = 2.0 Hz, 1H), 7.25 - 7.17 (m, 1H), 7.01 (dd, J = 8.3, 2.0 Hz, 1H), 6.90 (d, J = 8.3 Hz, 1H), 2.56 (s, 3H).

[0182] Compared to commonly used industrial synthesis methods, the synthesis of PY151 from anthranilic acid is industrially attractive because it comprises a convergent synthetic route that utilizes industrially acceptable temperature conditions. Furthermore, this synthetic process offers satisfactory reaction yields and simple purification steps, with the generated effluents being easily treated.

Claims

DEMANDS 1. Use of anthranilic acid in a process for preparing a compound selected from copper phthalocyanine, quinacridone, 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide, and 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid.

2. Use according to claim 1 in a process for preparing copper phthalocyanine, characterized in that said process comprises the following steps: a1) reacting anthranilic acid with sodium nitrite and sulfuric acid in aqueous solution, followed by the addition of a cyanide salt to obtain 2-cyanobenzoic acid; a2) reacting 2-cyanobenzoic acid with copper chloride, urea, and ammonium molybdate in a solvent; and a3) recovering copper phthalocyanine.

3. Use according to claim 2, wherein step a1) comprises reacting anthranilic acid with sodium nitrite and sulfuric acid in aqueous solution followed by adding a mixture of sodium cyanide and copper cyanide at a temperature of about 0 °C; and step a2) comprises reacting 2-cyanobenzoic acid with copper chloride, urea, and ammonium molybdate in Tanisole at a temperature between 100 and 200 °C, for 8 to 24 hours.

4. Use of anthranilic acid in a process for the preparation of 2-cyanobenzoic acid, said process comprising the following steps: a) reacting anthranilic acid with sodium nitrite and sulfuric acid in aqueous solution, followed by the addition of a cyanide salt, in particular a mixture of sodium cyanide and copper cyanide, preferably at a temperature of about 0 °C; and a') recovering 2-cyanobenzoic acid.

5. Use according to claim 1 in a process for preparing quinacridone, characterized in that said process comprises the following steps: bl) reacting anthranilic acid with benzoquinone to obtain 2,2'-((3,6-dioxocyclohexa-l,4-diene-l,4-diyl)bis(azanediyl))dibenzoic acid; b2) the reaction of 2,2'-((3,6-dioxocyclohexa-l,4-diene-l,4-diyl)bis(azanediyl))dibenzoic acid with phosphoric anhydride to obtain quinacridonequinone; b3) the reaction of quinacridonequinone with zinc to obtain 6,13-dihydroquinacridone; b4) the reaction of 6,13-dihydroquinacridone with sodium 3-nitrobenzenesulfonate; and b5) the recovery of quinacridone.

6. Use according to claim 5, wherein step b1) comprises reacting anthranilic acid with benzoquinone in a solvent at a temperature between 50 and 100 °C, for 12 to 24 hours; and step b2) comprises reacting 2,2'-((3,6-dioxocyclohexa-l,4-diene-l,4-diyl)bis(azanediyl))dibenzoic acid in a mixture of trifluoroacetic acid and methanesulfonic acid with phosphoric anhydride at a temperature between 40 and 100 °C, for 12 to 24 hours.

7. Use according to claim 1 in a process for preparing 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide, characterized in that said process comprises the following steps: c1) obtaining o-anisidine from anthranilic acid; c2) obtaining p-nitro-o-anisidine from o-anisidine; c3) obtaining N-(2-methoxyphenyl)-3-oxobutanamide from o-anisidine; c4) obtaining 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide by coupling p-nitro-o-anisidine with N-(2-methoxyphenyl)-3-oxobutanamide; and c5) the recovery of 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutaamide.

8. Use according to claim 7, wherein step cl) comprises the following steps: cia) reacting anthranilic acid with sulfuric acid and a sodium nitrite solution at a temperature between 90 and 130 °C for 5 to 60 minutes to obtain salicylic acid; clb) the reaction of salicylic acid with potassium carbonate and dimethyl sulfate at a temperature between 40 and 80 °C for 12 to 24 hours to obtain methyl 2-methoxybenzoate; clc) the reaction of methyl 2-methoxybenzoate with hydroxylamine and potassium hydroxide to obtain N-hydroxy-2-methoxybenzamide; cld) the reaction of N-hydroxy-2-methoxybenzamide with potassium carbonate and acetic anhydride at a temperature between 70 and 110 °C for 2 to 6 hours; i and cle) the recovery of o-anisidine.

9. Use according to claim 7 or 8, wherein step c2) comprises the following steps: c2a) reacting o-anisidine with acetic acid at a temperature between 90 and 140 °C for 12 to 20 hours to obtain N-(2-methoxyphenyl)acetamide; c2b) reacting N-(2-methoxyphenyl)acetamide with acetic anhydride and nitric acid at a temperature between 20 and 40 °C to obtain N-(2-methoxy-4-nitrophenyl)acetamide; and c2c) reacting N-(2-methoxy-4-nitrophenyl)acetamide in a sodium hydroxide solution at a temperature between 70 and 110 °C for 12 to 24 hours; and c2d) recovering p-nitro-o-anisidine.

10. Use according to any one of claims 7 to 9, wherein step c3) comprises reacting o-anisidine with ethyl acetoacetate and pyridine at a temperature between 90 and 130 °C for 12 to 20 hours.

11. Use according to any one of claims 7 to 10, wherein step c4) comprises reacting an aqueous solution of p-nitro-o-anisidine and sodium nitrite with an aqueous solution of N-(2-methoxyphenyl)-3-oxobutanamide at a temperature between 15 and 25 °C for 1 to 6 hours.

12. Use according to claim 1 in a process for preparing 2-({2-oxo-l- [(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid, characterized in that said process comprises the following steps: d1) obtaining 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one from anthranilic acid; and d2) reacting 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one with the diazonium salt of anthranilic acid; and d3) recovering 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid.

13. Use according to claim 12, wherein step dl) comprises the following steps: dla) reacting anthranilic acid with sulfuric acid in a refluxing solvent for 12 to 20 hours, preferably about 16 hours, to obtain methyl anthranilate; dlb) reacting methyl anthranilate with bis(hydroxylammonium) sulfate and followed by the addition of a sodium sulfite solution to obtain hydroxamic anthranilic acid; dlc) reacting hydroxamic anthranilic acid with ethyl chloride oformiate in a basic solution at a temperature between 10 and 35 °C, preferably about 20 °C, for 1 to 4 hours, preferably about two hours, to obtain 1,3-dihydrobenzimidazol-2-one;did) the reaction of 1,3-dihydrobenzimidazol-2-one with sulfuric acid and nitric acid at a temperature between 0 and 15 °C, preferably about 5 °C to obtain 5-nitro-1,3-dihydrobenzimidazol-2-one; die) the reaction of 5-nitro-1,3-dihydrobenzimidazol-2-one with palladium on carbon and ammonium formate in a solvent for 30 minutes to 12 hours, preferably about 1 hour to obtain 5-amino-1,3-dihydrobenzimidazol-2-one; dlf) the reaction of 5-amino-1,3-dihydrobenzimidazol-2-one with 2,2,6-trimethyl-4H-1,3-dioxine-4-one in refluxing water for 30 minutes to 3 hours; and dig) the recovery of 5-acetoacetamido-l-3-dihydrobenzimidazol-2-one.; 14. Use of anthranilic acid in a process for the preparation of 1,3-dihydrobenzimidazol-2-one, said process comprising the following steps: dla) the reaction of anthranilic acid with sulfuric acid in a solvent under reflux for 12 to 20 hours, preferably about 16 hours, to obtain methyl anthranilate; dlb) the reaction of methyl anthranilate with bis(hydroxylammonium) sulfate and followed by the addition of a sodium sulfite solution to obtain hydroxamic anthranilic acid; dlc) the reaction of hydroxamic anthranilic acid with ethyl chloride oformiate in a basic solution at a temperature between 10 and 35 °C, preferably about 20 °C, for 1 to 4 hours, preferably about two hours, to obtain 1,3-dihydrobenzimidazol-2-one; and dl') the recovery of 1,3-dihydrobenzimidazol-2-one.

15. Use according to any one of claims 1 to 14, wherein anthranilic acid is produced from a microorganism, in particular a bacterium, preferably of the species Escherichia coli.

16. Copper phthalocyanine comprising a percentage of modern carbon equal to or greater than 80%, preferably equal to or greater than 87.5%, even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640.

17. Copper phthalocyanine according to claim 16 obtained by a process or method of preparation comprising or consisting of the following steps: a) the culture of a microorganism, in particular of the species E. coli, to produce anthranilic acid; a) the reaction of anthranilic acid with sodium nitrite and sulfuric acid in aqueous solution, followed by the addition of a cyanide salt to obtain 2-cyanobenzoic acid; a2) the reaction of 2-cyanobenzoic acid with copper chloride, urea, and ammonium molybdate in a solvent; and a3) the recovery of copper phthalocyanine.

18. 2-Cyanobenzoic acid comprising a percentage of modern carbon equal to or greater than 70%, preferably equal to or greater than 80%, even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to the standard NF EN 16640.

19. 2-Cyananobenzoic acid according to claim 18 obtained by a process or method of preparation comprising or consisting of the following steps: a0) the culture of a microorganism, in particular of the species E. coli, to produce anthranilic acid; a1) the reaction of anthranilic acid with sodium nitrite and sulfuric acid in aqueous solution, followed by the addition of a cyanide salt, in particular a mixture of sodium cyanide and copper cyanide, preferably at a temperature of about 0 °C; and a2) the recovery of 2-cyanobenzoic acid.

20. Quinacridone comprising a percentage of modern carbon equal to or greater than 60%, preferably equal to or greater than 70%, even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640.

21. Quinacridone according to claim 20 obtained by a process or method of preparation comprising or consisting of the following steps: b1) the culture of a microorganism, in particular of the species E. coli, to produce anthranilic acid; b2) the reaction of anthranilic acid with benzoquinone to obtain 2,2'-((3,6-dioxocyclohexa-1,4-diene-1,4-diyl)bis(azanediyl))dibenzoic acid; b2) the reaction of 2,2'-((3,6-dioxocyclohexa-1,4-diene-1,4-diyl)bis(azanediyl))dibenzoic acid with phosphoric anhydride to obtain quinacridonequinone; b3) the reaction of quinacridonequinone with zinc to obtain 6,13-dihydroquinacridone; b4) the reaction of 6,13-dihydroquinacridone with sodium 3-nitrobenzenesulfonate; and b5) the recovery of quinacridone.

22. 2-[(2-Methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanametamide comprising a percentage of modern carbon equal to or greater than 60%, preferably equal to or greater than 66.5%, preferably equal to or greater than 77.5%, and even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640.

23. 2-[(2-Methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutananamide according to claim 22 obtained by a process or method of preparation comprising or consisting of the following steps: c1) the culture of a microorganism, in particular of the species E. coli, to produce anthranilic acid; c2) the obtaining of o-anisidine from anthranilic acid; c3) the obtaining of p-nitro-o-anisidine from o-anisidine; c4) the obtaining of N-(2-methoxyphenyl)-3-oxobutananamide from o-anisidine; c4) obtaining 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide by coupling p-nitro-o-anisidine with N-(2-methoxyphenyl)-3-oxobutanamide; and c5) recovering 2-[(2-methoxy-4-nitrophenyl)diazenyl]-N-(2-methoxyphenyl)-3-oxobutanamide.

24. 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid comprising a percentage of modern carbon equal to or greater than 60%, preferably equal to or greater than 77.5%, and even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640.

25. 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl)benzoic acid according to claim 24 obtained by a process or method of preparation comprising or consisting of the following steps: d) culturing a microorganism, in particular of the species E. coli, to produce anthranilic acid; d) obtaining 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one from anthranilic acid; and d2) the reaction of 5-acetoacetamido-l,3-dihydrobenzimidazol-2-one with the diazonium salt of anthranilic acid; and d3) the recovery of 2-({2-oxo-l-[(2-oxo-2,3-dihydro-lH-benzimidazol-5-yl)carbamoyl]propyl}diazenyl) benzoic acid.

26. 1,3-Dihydrobenzimidazol-2-one comprising a percentage of modern carbon equal to or greater than 90%, preferably equal to or greater than 95%, and even more preferably equal to or greater than 99%, the percentage of modern carbon being determined by accelerator mass spectrometry according to standard NF EN 16640.

27. l,3-Dihydrobenzimidazol-2-one according to claim 26 obtained by a process or method of preparation comprising or consisting of the following steps: dO) the culture of a microorganism, in particular of species E.Coli, to produce anthranilic acid; dla) the reaction of anthranilic acid with sulfuric acid in a solvent under reflux for 12 to 20 hours, preferably about 16 hours, to obtain methyl anthranilate; dlb) the reaction of methyl anthranilate with bis(hydroxylammonium) sulfate and followed by the addition of a sodium sulfite solution to obtain hydroxamic anthranilic acid; dlc) the reaction of hydroxamic anthranilic acid with ethyl chloride oformiate in a basic solution at a temperature between 10 and 35 °C, preferably about 20 °C, for 1 to 4 hours, preferably about two hours; and dl') the recovery of 1,3-dihydrobenzimidazol-2-one.

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