Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C253/00—Preparation of carboxylic acid nitriles

Definitions

• the present invention relates to a method of manufacturing diaminomaléonitril ⁇ .
• Diaminomaléonitriie (DA N) is known to be a precursor for the synthesis of nitrogenous rings such as imidazotes, pyrazines and purines. But recently the DAMN has proved to be a precursor for the synthesis of new lithium salts having interesting properties for improving the performance of Li-ion batteries (WO 2010/023413),
• Diaminomaléonitriie is conventionally obtained by polymerization of cyanhydric acid (HCN) using different types of catalysis.
• GB 1325620 describes the preparation of DAMN by tetramerization liquid phase HCN at a temperature between ⁇ ⁇ 40 ° C and below 0 ° C in the presence of a basic catalyst and at least one catalyst selected from-eo cyanogen and diiminosuccinonitrile.
• US Pat. No. 3,839,406 describes a process for the preparation of the DAMN comprising the following steps: (a) mixing at ambient temperature an alkaline catalyst chosen from sodium cyanide and potassium cyanide, in a solvent chosen from hexa-methyl-phosphoramide and hexa-ethylphosphoramide, (b) progressive addition of HCN and continued agitation of the reaction medium! for six hours with a molar ratio cyanide aleaisn / HCN less than 0.25, (c) dilution of the solution with hot water and (d) removal of a blackish amorphous polymer by flitration.
• an alkaline catalyst chosen from sodium cyanide and potassium cyanide
• the document CA 1000297 describes a process for the manufacture of diaminomalonitriy by polymerization of HCN in the presence of a compound chosen from oxides, hydroxides and cyanides of alkaline earth metals in a solvent chosen from n- methylpyrrolidone, dimethylsulfoxide and dimethylformamide.
• the starting reagent is hydrocyanic acid, which is a very toxic gas and whose use is highly regulated, which therefore limits access to the DAMN.
• the growing market for Li-ion batteries and interesting properties of the lithium salts synthesized from the DAMN will induce a high demand of DA N,
• the present invention relates to a process for producing diaminomalononitrile from a cyanohydrin ketone according to reaction 1.
• R and R ' identical or different, representing a linear or branched alkyl chain having from 1 to 5 carbon atoms.
• the process according to the present invention comprising at least one reaction step (1) can be carried out in the presence of a catalyst.
• the catalyst may be selected from the group consisting of inorganic or organic bases of which pK A is from 1 to 14, alkali or alkaline earth metal oxides and Lewis acids.
• Oxides that may be mentioned include potassium oxide, sodium oxide or calcium oxide. Silicon oxide may also be suitable.
• Lewis acids examples include trialkylaluminum, boron trialkyl or pentaalkylphosphorus.
• reaction can be carried out in the presence of an aprotic solvent.
• aprotic solvent mention may be made of nitriies, hexa-alkylphosphoramide, dimethylformamide, dimethylsulfoxide, toluene or oxyfene.
• the additives may also be present in the reaction medium.
• additives mention may in particular be made of mercaptans.
• the reaction temperature may be from -50 to 200 ° C, preferably from -20 to 150 ° C.
• reaction time can vary within wide limits. It is preferably between 1 and 96 hours, advantageously 1 and 72 hours. According to one embodiment of the process of the present invention, reaction 1 can be carried out in the presence of HCN according to the following scheme,
• the molar ratio of HCN / ketone cyanohydrin y / x may be between 0.001 and 2.5, preferably between 0.005 and 2.
• the molar ratio of the amount of catalyst to the total amount of reagents involved is preferably between 0.01 and 1,
• the method according to the present invention may further comprise at least one step of recovering the ketone formed as a co-product.
• the process may also include at least one catalyst recovery step.
• the process may also include a step of recovering excess cyanohydrin ketone.
• the process may comprise a step of purifying the diaminomaleonitile such as, for example, recrystallization or treatment with activated charcoal.
• the ketone cyanohydrin is acetone cyanohydrin.
• Example 1 illustrates the invention without limiting it.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 2012
  • 2012-07-17 FR FR1256893A patent/FR2993560B1/fr not_active Expired - Fee Related
• 2013
  • 2013-06-14 US US14/415,003 patent/US20150197487A1/en not_active Abandoned
  • 2013-06-14 CN CN201380036061.7A patent/CN104411680A/zh active Pending
  • 2013-06-14 WO PCT/FR2013/051395 patent/WO2014013151A1/fr active Application Filing
  • 2013-06-14 EP EP13737315.5A patent/EP2874995A1/de not_active Withdrawn
  • 2013-06-14 JP JP2015522140A patent/JP2015528803A/ja active Pending

Non-Patent Citations (1)

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