Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
  • C07C229/46—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino or carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
  • C07C211/16—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings other than six-membered aromatic rings
  • C07C211/19—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings other than six-membered aromatic rings containing condensed ring systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
  • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
  • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
  • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
  • C07C215/20—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated the carbon skeleton being saturated and containing rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2602/00—Systems containing two condensed rings
  • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
  • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

Definitions

• the present invention discloses novel norbornane-based methylene amine compounds as well as a method for making them comprising nitrile hydrogenation reactions.
• Cycloaliphatic compounds containing methylene amine groups are of great interest as precursors to a variety of useful molecules with applications as monomers for the production of polymers, as starting materials for organic synthesis or as epoxy curing agents, either neat or as the adducted form.
• One skilled in the art of epoxy formulation will select different curing agents based on their structure to control curing time, pot life and physical properties of resulting coatings, adhesives, castings or composites.
• the methylene amine functional group can also be utilized in organic synthesis, and treatment with acids can yield ammonium salts, which may be useful as surfactants and detergents.
• Norbornane based methylene amine compounds are an important class of cycloaliphatic amines.
• Norbornane dimethyleneamine was described in US 3143570 in 1964 and its use has been reported in a variety of applications including preparation of isocyanates (JP 2764081 ) and in polyurethane foams (JP 2764081 ) since that time.
• this amine compound little work has been invested in the modification of the norbomyl skeleton with an exception of norbornyl structures bearing a fused 5-member alicyclic ring, i.e. thcyclodecane structures derived from dicyclopentadiene (NL 64014369).
• GB1480999 describes the preparation and use of triamines based on the norbornane skeleton as isocyanate precursors for polyurethane lacquer formation, but fails to suggest the novel structures reported, herein.
• R 20 , R 21 , R 22 can be the same or different and are each independently H, a Ci to C 20 alkyl group, a C 1 to C 20 alkyl group substituted with a hydroxyl group, a Ci to Ci 8 perfluoroalkyl group, a phenyl group, a C & to C 2 o aryl group substituted with a Ci to Ci 2 alkyl group, a Ce to C 2 o aryl group substituted with a hydroxyl group, a C(O)OR 29 group (with R 29 selected to be a Ci to C 20 linear or branched or cyclic alkyl group or a C 6 to C 20 aryl group), or an alkylene chain (-(CH 2 ) q -; q equals an integer 0-16) or nothing (in which case A or B may connect back to the norbornane skeleton), with the proviso that R 20 , R 21 and R 22 do not comprise a cyano group or an amino group and
• B equals -CN, -CH 2 NH 2 , -(CH 2 ) S OH or — C(O)OR 24 with s equal to an integer 0-12 and with R 24 selected to be H, a Ci to C 20 linear or branched or cyclic alkyl or alkylene group, a C 6 -C 20 aryl group or a Ci-Ci 8 perfluorinated alkyl group and wherein R 24 may connect to the norbornane skeleton through R 20 , R 21 or R 22
• R 25 , R 26 , R 27 , R 28 can be the same or different and are each independently H or — CH 2 NH 2 , with the proviso that three of R 25 , R 26 , R 27 , R 28 are each H.
• the relative spatial orientation of the substituents on the norbornane skeleton can be any possible combination. Stereoisomeric mixtures are common embodiments of the invention.
• PM505USNA the disclosure of which is incorporated by reference herein in its entirety
• a catalyst and optionally a promoter at a temperature of about 60 0 C to about 200 0 C and a pressure of 340 kPa - 17240 kPa to yield norbornane methylene amine derivatives of the formula (I), wherein the catalyst comprises a transition metal, preferably cobalt or nickel.
• the present invention provides a hydrogenation method for preparing norbornane derivatives, which contain methylene amine groups.
• the present method yields the present norbornane methylene amine derivatives as a mixture of isomers, because the starting feed may have a mixture of isomers.
• both the individual compounds and also the mixtures of isomers thereof are within the scope of the present invention.
• the method for making the compounds of the present invention involves a hydrogenation process of nitrile containing molecules.
• precursor norbornane nitrile derivatives as described in the inventors' concurrently filed U.S. Patent Application Ser. No. 10/760,779, filed
• Hydrogen is preferably used in excess. Hydrogen pressures are generally in the range of about 340 kPa - 17240 kPa, with about 1480 to about 9000 kPa preferred.
• the hydrogenation process can be conducted at temperatures from 50 0 C to about 18O 0 C, preferably from 65 0 C to about 100 0 C.
• Preferred catalysts for hydrogenating nitriles to amines comprise one or more elements from the series of transition metals, particularly useful are iron, cobalt, nickel, ruthenium, rhodium and combinations thereof.
• the hydrogenation catalyst may also comprise one or more elements in addition to the transition metals mentioned above, for example, elements of Group IA (including lithium, sodium and potassium), elements of Group MA (including magnesium and calcium), titanium, elements of Group Vl (including chromium, molybdenum and tungsten), elements of Group VIII (including palladium) and/or aluminum, silicon, boron and/or phosphorous.
• the hydrogenation catalyst can also be in the form of an alloy, including a solid solution of two or more elements.
• the hydrogenation catalyst can also be a homogeneous catalyst capable of hydrogenating nitriles to amines, e.g. HRh(PPh 3 )4 or HbRu(HbMPCy S ⁇ .
• the transition metal for hydrogenation can also be supported on an inorganic support such as alumina, magnesium oxide and combinations thereof.
• the metal can be supported on an inorganic support by any means known to one skilled in the art such as, for example, impregnation, co-precipitation, ion exchange, or combinations of two or more thereof.
• the metal can be reduced before the hydrogenation reaction by any means known to one skilled in the art such as, for example, pretreatment with hydrogen, formaldehyde or hydrazine.
• the hydrogenation catalyst can be present in any appropriate physical shape or form. It can be a homogeneous catalyst, a heterogenized homogeneous catalyst or it can be in fluidizable forms, powders, extrudates, tablets, spheres or combinations of two or more thereof.
• the hydrogenation catalyst may be in sponge metal form, for example, the Raney® nickels and Raney® cobalts.
• the molar ratio of hydrogenation catalyst to feed i.e. nitrile molecules such as those described in the previously mentioned concurrently filed U.S. Patent Application Ser. No. 10/760,779, filed January 19, 2004 (Attorney docket no. PI-1505USNA) either alone or in mixtures of isomers
• the weight ratio of hydrogenation catalyst to feed is generally in the range of from about 0.0001 :1 to about 1 :1 , preferably about 0.001 :1 to about 0.5:1.
• the catalytic element is supported on an inorganic support or is a portion of an alloy or solid solution, the catalytic element is generally present in the range of from about 0.1 to about 60, preferably about 1 to about 50, and most preferably about 2 to about 50 weight percent based on the total hydrogenation catalyst weight.
• the preferred nitrile hydrogenation catalyst is a sponge metal type catalyst.
• the metallic component is iron, cobalt, nickel or combinations thereof.
• Commercially available catalysts of this type are promoted or un- promoted Raney® Ni or Raney® Co catalysts that can be obtained from the W. R. Grace and Co. (Chattanooga, TN), or alternative sponge metal catalysts available, for example, from Activated Metals Corporation (Sevierville, TN) or Degussa (Parsippany, NJ).
• the hydrogenation can optionally be conducted in the presence of a solvent.
• Suitable solvents include those known in the art as useful for hydrogenation reactions. Examples of these are amines, aliphatic alcohols, aromatic compounds, ethers, esters (including lactones), and amides (including lactams). Specific examples of solvents include: ammonia, toluene, tetrahydrofuran, methanol, ethanol, any isomeric propanol, any isomeric butanol and water. Preferred solvents include ammonia and methanol. It will be appreciated that the solvent may serve to reduce the viscosity of the system to improve fluidity of the catalyst in the reaction vessel, as well as serve to remove the heat of reaction from the feed and products.
• the solvent may be present in a range of 1 % to 75% by weight of the total reaction mixture, excluding the catalyst, preferably from 10% to 50%.
• a promoter may be used in the hydrogenation process to alter the rate of the reaction and / or to alter the selectivity of the reaction.
• Suitable promoters include water, alkali or alkaline earth metal hydroxides, quaternary ammonium hydroxides, quaternary ammonium cyanides, quaternary ammonium fluorides, and combinations of these. Promoters may be present at from 10 ppm to 3% by weight of the total reaction mixture, excluding the catalyst, preferably from 50 ppm to 1.5%.
• any olefin content of feed i.e. any carbon-carbon double bonds in the structure
• the preferred catalyst for hydrogenation of the olefin comprises palladium, rhodium, nickel and / or ruthenium. Hydrogenation of the olefin content can occur before, during or after the hydrogenation of the nitrile content to amine.
• the cycloaliphatic compounds used as starting material in this invention contain a nitrile substituted norbornane (bicyclo[2.2.1]heptane) fragment which is hydrogenated using the hydrogenation process of this invention to the products of this invention, the norbornane amine derivatives.
• the norbornane nitrile starting materials can be prepared as described in the inventors previously mentioned concurrently filed U.S. Patent Application Ser. No. 10/760,779, filed January 19, 2004 (Attorney docket no. PI-1505USNA).
• the present invention relates to compounds with the general structure of formula (III):
• R >22 can vary and mixtures of compounds and isomers are commonly produced by this invention.
• Preferred norbornane methylene amine derivatives in this embodiment are for example structures (IV - Xl):
• the norbornane nitrile derivative is reacted with hydrogen in the presence of a catalyst, preferably cobalt and optionally a promoter.
• a product mixture is obtained which generally comprises norbornane derivatives having two methylene amine groups.
• the present invention relates to compounds with the general structure of formula (XII):
• Preferred norbornane methylene amine derivatives in this embodiment are for example structures (XIII - XVI):
• the norbornane nitrile derivative is reacted with hydrogen in the presence of a group VIII catalyst, preferably cobalt and optionally a promoter.
• a product mixture is obtained which generally comprises norbornane derivatives having one methylene amine group and one or more ester groups.
• the present invention relates to compounds with the general structure of formula (XVII, XIX - XXI):
• the norbomane nitrile derivative is reacted with hydrogen in the presence of a group VIII catalyst, preferably cobalt, and optionally a promoter.
• a product mixture is obtained which generally comprises norbomane derivatives having one or two methylene amine groups and in case of (XIX) a lactone group and in the case of (XX) and (XXI) alcohol groups.
• ester groups of (XII) - (XVI) and (XIX) and the anhydride group of (XVIII) may be converted to alcohol groups by methods known in the art, e.g.
• Preferred norbomane based methylene amine derivatives in this embodiment are for example structures (XXIII - XXIV):
• the norbomane nitrile derivative is reacted with hydrogen in the presence of a group VIII catalyst, preferably cobalt and optionally a promoter.
• a product mixture is obtained which generally comprises norbomane derivatives having two methylene amine groups.
• the present invention relates to compounds with the structure of formulae (XXV) and (XXVII):
• the norbomane nitrile derivative is reacted with hydrogen in the presence of a group VIII catalyst, preferably cobalt and optionally a promoter.
• a product mixture is obtained which generally comprises norbomane derivatives having two methylene amine groups.
• the products according to the present invention can be used as organic synthesis starting materials, monomers for the production of polymers, as epoxy curing agents or in surfactant applications.
• Example 1 Hydrogenation of 2-(2-cyanoethyl)-(5 or 6)-cyano- bicyclo[2.2.1]heptane (mixture of isomers).
• To a 100cc pressure reactor were added 40g of starting dinitrile, 2g of Raney® Co 2724 slurry, and 2g methanol (to aid in transfer). The reactor was sealed, purged with hydrogen and tested for leaks and cooled. Ammonia (17g) was added by distillation from a cylinder. The reactor was heated to 75°C at which point the pressure was increased to 6205 kPa (900 psig) with hydrogen and the reaction commenced. Hydrogen was constantly replenished from a 1 L pressure vessel and controlled by a forward pressure regulator.
• Example 2 Hydrogenation of 2-methyl-2, (5 or 6)dicyano- bicyclo[2.2.1]heptane (mixture of isomers).
• To a 4 L pressure reactor were added 90Og of starting dinitrile, 9Og of Raney® Co 2724, approximately 9Og water, and 32Og methanol (to aid in transfer). The reactor was sealed, purged with hydrogen and tested for leaks and cooled. Ammonia (600g) was added by distillation from a cylinder. The reactor was heated to 80 0 C at which point the pressure was increased to 8273 kPa (1200 psig) with hydrogen and the reaction commenced. Hydrogen was constantly replenished from a cylinder and controlled by a forward pressure regulator. After 7 hours the reaction was cooled.
• Example 3 Hydrogenation of 1 ,2, 3,4,4a, 5,6,7,8,8a-decahydro-2-methyl- 1 ,4:5,8-Dimethanonaphthalene-2, (6 or 7)-dicarbonitrile.
• 77Og starting dinitrile 77g of Raney® Co 2724, approximately 8Og water, and 70Og methanol (to aid in transfer).
• the reactor was sealed, purged with hydrogen and tested for leaks and cooled.
• Ammonia (50Og) was added by distillation from a cylinder.
• the reactor was heated to 8O 0 C at which point the pressure was increased to 8273 kPa (1200 psig) with hydrogen and the reaction commenced.
• Example 4 Hydrogenation of 1 ,2, 3,4,4a, 5,6,7,8,8a-decahydro-2-methyl- 1 ,4:5,8-Dimethanonaphthalene-2, (6 or 7)-dicarbonitrile.
• a 1 L pressure reactor were added 147g starting dinitrile, 15g of Raney® Co 2724, approximately 22g water, and 20Og methanol (to aid in transfer).
• the reactor was sealed, purged with hydrogen and tested for leaks and cooled.
• Ammonia (15Og) was added by distillation from a cylinder.
• the reactor was heated to 85°C at which point the pressure was increased to 8273 kPa (1200 psig) with hydrogen and the reaction commenced.
• Example 5 Hydrogenation of 2-ethyl-3-((5 or 6)-cyano-bicyclo[2.2.1.]hept- 2-yl)-(5 or 6)-cyano-bicyclo[2.2.1]heptane (mixture of isomers).
• To a 4 L pressure reactor were added 55Og of the starting dinitrile, 55g of Raney® Co 2724, approximately 5Og water, and 50Og methanol (to aid in transfer). The reactor was sealed, purged with hydrogen and tested for leaks and cooled. Ammonia (50Og) was added by distillation from a cylinder. The reactor was heated to 85°C at which point the pressure was increased to 8273 kPa (1200 psig) with hydrogen and the reaction commenced.
• Example 6 Hydrogenation of 2-methyl-2, (5 or 6)-dicyano- bicyclo[2.2.1]heptane (mixture of isomers).
• To a 100cc pressure reactor were added 15g starting dinitrile, 2g of Raney® Ni 2400, 4g water, 3Og methanol and 0.06g 50% NaOH(aq). The reactor was sealed, purged with hydrogen and tested for leaks. It was heated to 75°C at which point the pressure was increased to 3447 kPa (500 psig) with hydrogen and the reaction commenced. Hydrogen was constantly replenished from a 1 L pressure vessel and controlled by a forward pressure regulator. After 6.5 hours the reaction had consumed 0.26 mol H 2 from the reservoir and the reaction was cooled.
• Example 7 Hydrogenation of 2-((3 or 4)-cyanocyclohex-1-yl) -(5 or 6)- cyano- bicyclo[2.2.1]heptane (mixture of isomers).
• 2-((3 or 4)-cyanocyclohex-1-yl) -(5 or 6)-cyano- bicyclo[2.2.1]heptane 3g of Raney® Co 2724 slurry, and 2Og tetrahydrofuran.
• the reactor was sealed, purged with hydrogen and tested for leaks and cooled.
• Ammonia (2Og) was added by distillation from a cylinder.
• the reactor was heated to 75°C at which point the pressure was increased to 6205 kPa (900 psig) with hydrogen and the reaction commenced. Hydrogen was constantly replenished from a cylinder and controlled by a forward pressure regulator. After 3 hours the reaction was cooled. An infrared spectrum of the product revealed no nitrile stretching absorbance (2235 cm “1 ) but the presence of amine N-H stretching bands around 3365cm “1 and 3285cm “1 . NMR spectra were consistent with formation of the diamine product, (XXV), as well.
• Example 8 Hydrogenation of 2-cyano-5,6- di(methoxycarbonyl)bicyclo[2.2.1]heptane.
• To a 100cc pressure reactor were added 25.1g of starting nitrile diester, 4g of Raney® Co 2724 slurry, and 30.6g methanol. The reactor was sealed, purged with hydrogen and tested for leaks. The reactor was heated to 70 0 C at which point the pressure was increased to 3447 kPa (500 psig) with hydrogen and the reaction commenced. Hydrogen was constantly replenished from a cylinder and controlled by a forward pressure regulator. After 4 hours the reaction was stopped.
• Example 9 Hydrogenation of 2-(hydroxymethyl)-(5 or 6)-cyano- bicyclo[2.2.1]heptane-2-ethanol.
• a 100cc pressure reactor were added 9.Og of starting nitrile diol, 2g of Raney ® Co 2724 slurry, and 21 g methanol.
• the reactor was sealed, purged with hydrogen and tested for leaks.
• Ammonia (2Og) was added by distillation from a cylinder.
• the reactor was heated to 7O 0 C at which point the pressure was increased to 6205 kPa (900 psig) with hydrogen and the reaction commenced.
• Examples 10 - 14 Methylene amines of this invention were reacted with a typical epoxy resin to prepare films.
• Bis(4-glycidyloxyphenyl)methane (Aldrich) was placed in a reaction vial.
• a di-amine of this invention in a mol ratio of 2:1 at room temperature. This mixture was mixed using a Vortex mixer for 2 minutes. The homogenous clear mixture was drawn out onto a glass plate and placed into the dry time recorder. The dry time recorder was set to a 24 hour cycle and the measurement was carried out at room temperature.
• Stage 0 leveling
• Stage 1 basic trace
• Stage 2 film building
• Stage 3 Surface trace
• Stage 4 dry
• Various modifications, alterations, additions or substitutions to the processes and compositions of this invention will be apparent to those skilled in the art without departing from the spirit and scope of this invention.
• This invention is not limited to the illustrative embodiments set forth herein, but rather is defined by the following claims.

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