Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
  • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/33—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings
  • C07C211/34—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton
  • C07C211/36—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton containing at least two amino groups bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
  • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated

Definitions

• Described herein is the selective, low pressure hydrogenation of 1-amino- 2-cyano-1-cyclopentene (CPI) to 2-(aminomethyl)-1-cyclopentylamine (AMC) by a combined catalyst system comprising nickel in combination with palladium on carbon, or a single palladium-doped Raney-type catalyst.
• CPI 1-amino- 2-cyano-1-cyclopentene
• AMC 2-(aminomethyl)-1-cyclopentylamine
• AMC is a valuable molecule that is useful in the formulation of epoxy- curing agents for polyurethane cross-linkers, for polyamide modifiers, for metal chelating agents and a host of other uses.
• AMC has been produced from CPI by various catalytic hydrogenation methods. Most of these prior art methods require high pressures of hydrogen, high levels of corrosive sodium hydroxide, or results in low AMC purity and/or yield.
• the combination of these improvements to AMC manufacture affords an easier operation and lower overall cost of production.
• a process for preparing 2-(aminomethyl)-1- cyclopentylamine comprising: (i) preparing an activated catalyst by combining a suitable solvent and a catalyst system in a vessel purged with an inert gas, pressurized with hydrogen to about 50-500 psi at a temperature of about 25 °C to about 50 °C, wherein said catalyst system comprises either nickel and palladium, wherein said palladium is supported on carbon, or palladium- doped Raney type nickel; (ii) contacting said activated catalyst with 1-amino-2- cyano-1-cyclopentene, at least an equimolar portion of anhydrous ammonia, and a solution of an aqueous inorganic base selected from the group consisting of sodium hydroxide, lithium hydroxide and potassium hydroxide; (iii) pressurizing the vessel by raising the temperature of the vessel to a temperature of about 50 °C to about 150 °C and a pressure
• AMC in the presence of (i) a dual, or combined, catalyst system comprising the combination of nickel with palladium, wherein the palladium is supported on carbon, or (ii) palladium-doped Raney-type nickel.
• the process is carried out at pressures of about 500 to about 1500 psi H2, temperatures of about 50 °C to about 150 °C, with added ammonia and inorganic aqueous base for about 1 to about 12 hours.
• the catalysts used herein are slurry-type particles and must be pre- activated in a suitable solvent system at a pressure of about 50 to about 500 psi H2, from about 25 to about 50 °C for about 1 to 4 hours prior to charging the CPI to the process.
• the starting 2-iminonitrile which is 1-amino-2-cyano-1- cyclopentene (CPI) is produced by the base catalyzed cyclization of adiponitrile. This method is disclosed in Thompson, Q.E.; J. Am. Chem. Soc, (1958), 80, 5483-5487.
• adiponitrile with a sterically hindered base, such as sodium t-butoxide (1:1 mole equivalent) in a non-polar aromatic solvent such as toluene, produces CPI in approximately 75% yield and greater than about 97% purity.
• a sterically hindered base such as sodium t-butoxide (1:1 mole equivalent)
• a non-polar aromatic solvent such as toluene
• Suitable catalysts for the low pressure hydrogenation of CPI include the combination of a nickel-containing catalyst, preferably unsupported metallic nickel or skeletal nickel (for example, Degussa Ni B113W, Raney Ni 2800) with about 5 to about 10 wt.% of palladium supported on carbon (for example, Heraeus K0236 10% palladium on carbon) or a single catalyst system of palladium-doped Raney Ni 2000.
• a nickel-containing catalyst preferably unsupported metallic nickel or skeletal nickel
• palladium supported on carbon for example, Heraeus K0236 10% palladium on carbon
• Pd-doped Raney Ni catalyst is preferred.
• the loading of palladium-on-carbon catalyst is about 5 - 20 wt.% relative to the nickel catalyst, which is equivalent to about 0.25-2 wt.% Pd relative to Ni.
• the level of palladium doping is about 0.25-1.0 wt.% relative to the nickel content, with about 0.5 wt.% being preferred.
• Slurry catalysts may be in the form of powder, granules, or other relatively fine particles while fixed-bed catalysts may be used as larger granules, extrudates, tablets, spheres, etc.
• Total catalyst loading relative to CPI is about 1g catalyst/10 g CPI, although higher loading may be required for increased rate of conversion.
• the catalyst is activated prior to use by combining it with water, an aprotic polar organic solvent, a combination of aprotic polar organic solvents, or a combination of aprotic polar organic solvent and water, preferably a solvent blend of dioxane / deionized water (about 3:1 v/v) in the reaction vessel, such as an autoclave, raising the temperature to approximately 25 °C to about 50 °C, purging with 2 volumes of N2, then adding hydrogen to a pressure of about 50 psi to about 500 psi. These conditions are held for about 1-4 hours to activate the catalyst system.
• the low-pressure hydrogenation is carried out in a reaction vessel the presence of hydrogen, typically between about 500 psi to about 1500 psi.
• Nitrogen or argon is initially used to remove air from the reaction vessel and can be added during the reaction to minimize the effects of trace oxygen on the nickel catalyst.
• the catalyst is contacted with CPI, at least an equimolar portion of anhydrous ammonia (about a 5/1 mole ratio NH3/CPI is preferred), and a solution of an aqueous inorganic
• Suitable bases include hydroxides of sodium, potassium and lithium.
• the reaction vessel where the hydrogenation is carried out is pressurized by raising the temperature of the vessel to a temperature of about 50 °C to about 150 °C and a hydrogen pressure of about 500 psi to about 1500 psi.
• the temperature and hydrogen pressure is maintained throughout the reaction to maintain catalyst life and to increase conversion and selectivity to AMC.
• Temperatures of about 50 °C to about 150 °C are preferred for the conversion of CPI to AMC during hydrogenation. It has been observed that higher temperatures of about 150 °C to about 200 °C result in unacceptably higher concentrations of secondary and tertiary amines.
• Suitable solvents include water, an aprotic polar organic solvent, a combination of aprotic polar organic solvents, or a combination of aprotic polar organic solvent and water. Examples of these include, but are not limited to dioxane, diethyl ether, tetrahydrofuran, water and combinations thereof.
• a solution comprising dioxane/water combination from about 1:1 v/v dioxane/water to about 5:1 v/v dioxane/water being preferred, with about 3:1 v/v dioxane/water being most preferred.
• the process is typically run in a stirred batch mode (slurry catalyst), where the catalyst is activated in the above procedure, after which the CPI, 50% aqueous inorganic base (approximately 2 wt.% of the solution relative to CPI) is charged to the autoclave.
• aqueous inorganic base may also be added as the inorganic base with a separate addition of water.
• the CPI that is used for the process of the present invention may be produced by contacting adiponitrile with a molar equivalent amount of a sterically hindered base in a non-polar, aromatic solvent. That CPI may be isolated and dissolved in dioxane/water solution.
• AMC is a useful molecule, for example, in the formulation of epoxy curing agents, for polyurethane cross-linkers, for polyamide modifiers, for metal chelating agents, etc.
• Example 1 Hydrogenation of 1-amino-2-cyano-1-cyclopentene (CPI) to 2- aminomethyl-cyclopentylamine (AMC) using a mixture of Nickel and Palladium/Carbon
• the reaction was agitated for 12 hours at 75 °C and 1500 psi of hydrogen, with re- pressuring of hydrogen during the reaction to maintain the pressure at 1500 psi +/- 100 psi.
• the reaction was cooled, vented and rinsed out with deionized water.
• the reaction mixture was filtered under an atmosphere of 2 through a coarse sintered glass filter funnel, and concentrated in vacuo to a clear, viscous, yellow oil.
• the oil was distilled using a Vigreaux column with fraction cutter, to collect product at 48 °C and 4 mm Hg pressure. Purity of the product by gas chromatography > 99%. Product yield was 65%.
• Example 2 Hydrogenation of CPI to AMC using a Palladium-promoted Raney 2000 Nickel
• Example 2 The same pre-treatment of catalyst was done as in Example 1 , with the exception that the catalyst was 0.5 wt.% palladium-promoted Raney Ni 2000.
• Pd/C were charged to a 100 cc autoclave.
• the mixture was pressurized to 300 psi with H 2 for 3 hours at 35 °C.
• the mixture was cooled to room temperature, vented, and then 5 g of CPI were added followed by 4 g of anhydrous ammonia.
• the vessel was pressurized to 1500 psi with H 2 at 150 °C (re-pressurizing as necessary) and heated for 6 hr.
• the mixture was then cooled to room temperature, vented, purged with 3 volumes of N 2 and analyzed by gas chromatography.
• the product was 92% unreacted CPI and 0% AMC.
• the vessel was pressurized to 1500 psi with H 2 at 150 °C (re-pressurizing as necessary) and heated for 6 hr. The mixture was then cooled to room temperature, vented, purged with 3 volumes of N 2 and analyzed by gas chromatography. The product contained 95% unreacted CPI and 0% AMC.
• Comparative Example 3 Hydrogenation CPI to AMC with 5% Pd/C to show the effects of not adding Ni, changing the solvent mixture to methanol, lowering the temperature and pressure
• Comparative Example 4 Hydrogenation of CPI to AMC with Ni to show the effect of not adding Pd, changing the solvent mixture to methanol, lowering the pressure

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