WO2004060866A2 - Procede de synthetisation d'amines a partir de nitriles - Google Patents

Procede de synthetisation d'amines a partir de nitriles Download PDF

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Publication number
WO2004060866A2
WO2004060866A2 PCT/US2003/041441 US0341441W WO2004060866A2 WO 2004060866 A2 WO2004060866 A2 WO 2004060866A2 US 0341441 W US0341441 W US 0341441W WO 2004060866 A2 WO2004060866 A2 WO 2004060866A2
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WO
WIPO (PCT)
Prior art keywords
catalyst
substrate
ratio
expressed
advantageously
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Application number
PCT/US2003/041441
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English (en)
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WO2004060866A3 (fr
Inventor
Philippe Marion
David Michael Lowe
Anthony F. Volpe, Jr.
Thomas Weskamp
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Rhodia Chimie
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Application filed by Rhodia Chimie filed Critical Rhodia Chimie
Priority to AU2003302339A priority Critical patent/AU2003302339A1/en
Publication of WO2004060866A2 publication Critical patent/WO2004060866A2/fr
Publication of WO2004060866A3 publication Critical patent/WO2004060866A3/fr

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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
    • 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
    • C07C209/52—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 imines or imino-ethers

Definitions

  • the present invention relates to a process for hydrogenating an imine function and a nitrile function.
  • it relates to the simultaneous hydrogenation (the latter term has the meaning of "per ormed in the same reaction medium"), of at least one imine function and at least one nitrile function carried by the same substrate.
  • diamines including cycloaliphatic diamines.
  • These diamines which are most often primary ones, are more specifically used for making polycondensates such as polyurea or polyamide or as an intermediate in the formation of is ⁇ cyanates, whether masked or not.
  • the most commonly used syntheses include a step for hydrogenating one or more nitrile f nctions.
  • the reduction, of the nitrile function involves a primary imine intermediate.
  • this function is more reducible than the nitrile function, the first hydrogenation being the factor, which limits kinetics, so that the intermediate imine amount is relatively small in the reaction media.
  • the coexistence within the reaction medium of a primary a ine function with an imine leads to the formation of an N-substituted imine (secondary one) which, after reduction, forms a secondary amine making up, in many cases, an impurity both undesirable and expensive to eliminate.
  • Another solution would be to use a catalyst for promoting the transition reaction from nitrile to amine, but the catalyst system should allow appropriate hydrogenation kinetics of the nitrile function without degrading the hydrogenation kinetics of the ketimine function.
  • the difficulty to overcome is that these properties are, to a large extent, conflicting.
  • reaction velocity and temperature play an important part. Specifically, as the temperature and the reduction duration increase, thermodynamic ratios tend to deviate from the most favorable ones or the required ones.
  • imine hydrogenation catalysts very often also behave as cis/trans iso erization catalysts. The latter aspect is particularly acute for cis/trans isomeries in cycloaliphatic amines.
  • the hydrogenation leads to a cis/trans isomery with respect to the nitrile function.
  • the ratio between the cis and trans forms is governed, on the one hand, by kinetics factors and on the other hand, by a thermodynamic characteristic related to the nitrile function.
  • IPDA IsoPhoroneDiAmine
  • Isophorone is a molecule resulting from the three- step condensation of acetone, which after adding a hydrocyanic acid molecule after condensation with ammonia and hydrogenation gives IPDA.
  • IPDA IPDA having a cis/trans ratio of about 3. Since it is easier to, decrease than to increase it, it is appropriate to aim at ratios that are greater or equal to this value.
  • Another object of the present invention s to provide a process of the above-mentioned kind for obtaining an IPDA yield (RR relative to isophorone nitrile) of at least 80%, advantageously 85%, and preferably 90%.
  • Another object of the present invention is to provide a process of the above-mentioned type, which allows, when applied to the synthesis of a cycloaliphatic polyamine, a cis/trans isomeric ratio to be obtained, which differs by at least 30%, and advantageously, by at least 100%, from the thermodynamic equilibrium at the reaction temperature.
  • Another object of the present invention is to provide a catalyst system, which enables accelerated kinetics of the hydrogenation reaction of nitrile functions by maintaining fast kinetics for hydrogenating the imine function.
  • Another object of the present invention is to provide a catalyst system of the above mentioned type, which allows treatment of a substrate carrying a nitrile function and an imine function, wherein the latter is formed in situ through the action of ammonia on ketone.
  • the effect is sensitive for substrate/catalyst ratios at least equal to 0,02 mole par gram of catalyst, advantageously from 0.03 to 0.3, preferably from 0.05 to 0.2
  • the preferred processing conditions are as follows:
  • Temperature from 40°C to 150 D C, and advantageously from 60° to 120°C (temperature is not required to be kept permanently at a single value chosen within this range and it may advantageously be programmed so as to increase while the reaction proceeds either continuously or stepwise) ;
  • Total pressure from 10 s to lQ 7 Pa, advantageously, from 2.10 s to 8.10 e Pa, and preferably from 2.10 s to 6.1C 6 Pa; - ⁇ H2 : from 5.10 5 to 9.10° Pa, and preferably from 3.10 G to 5.10 15 Pa;
  • - Ammonia/imine mole ratio at least two, and the upper limit is economic rather than technical but an upper limit for this ratio would be 100.
  • - Catalyst/substrate weight ratio at least 0.5%, and the upper limit is economic rather than technical, but an upper limit for this ratio would be of at most 50% (in particular for a continuous reaction) .
  • the reaction is performed in a liquid phase, advantageously in a solvent or a solvent system, the solvents being chosen from common solvents for nitrile hydrogenation .
  • these common solvents include alcohols, preferably primary ones, including in particular methanol, ethers, particularly cyclic ethers
  • the presence of water is very important.' In this regard, it is desirable that the [H 2 0] / [substrate] ratio of water, expressed in moles, to the imine function, expressed as an equivalent, be at least 1, advantageously 2, and preferably 3.
  • the ratio ( [NH 3 ] / [imine] ) of ammonia, expressed in moles, to the imine functions, expressed as an equivalent be at most 50, and advantageously 25.
  • said group VIII element-based catalyst (the periodic table of elements used in the present application is that given in the addition to the
  • Said Raney® type metal catalyst is a catalyst whose group VIII metal is advantageously cobalt or nickel, preferably cobalt.
  • the catalyst further contains aluminum, which originates from the starting mother alloy (it should be recalled that Raney® type catalysts are obtained through alkaline leaching of aluminum alloys, of the catalyst base metal and possibly, of all or part of the potentiator metals described below) ; it is alsc preferable that the potentiator metals having a redox potential, under the processing conditions of the invention, close to (that is in the inclusive range of
  • Aluminum is not considered as a potentiator agent in the present invention.
  • the atomic ratio of aluminum to the base metal in the catalysts is at most 1/3, and advantageously at most 1/4, preferably at most 1/5, and more preferably at most 10%.
  • the catalyst is potentiated by at least one, and preferably two element (s) other than the metal on which the catalyst is based. These elements are used or serve as co-catalysts and are chosen from the following group of elements: gallium, chromium, nickel, platinum group metals (in particular rhodium and iridiurr.) , hafnium, zirconium, lead, and tin.
  • said catalyst is then used in the presence of at least one element serving as a co-catalyst chosen from the above elements.
  • the atomic ratio [co- cat] /[cat] of each of the elements present as the co- catalyst to the base metal in the catalyst be at least 1/1000, and advantageously at least 5/1000. It is also desirable that the [co-cat] / [cat] atomic ratio of each of the elements present as the co-catalyst to the base metal in the catalyst be at most 1/10, and preferably, at most 1/20.
  • the [ ⁇ co-cat] / [cat] atomic ratio of the sum of the elements present as the co-catalyst (s) to the metal in the catalyst will be at least 2/1000, advantageously at -least 5/1000, and preferably at least
  • the preferred catalysts will include cobalt-based ones, among which those: containing at least chromium as a potentiator element; containing at least nickel as a potentiator element; and advantageously, containing at least both nickel and chromium as the potentiator elements . According to the present invention, it is suggested to use at least two distinct elements serving as the co- catalysts .
  • the co-catalyst elements may be introduced into the aluminum alloy comprising the raw material of the Raney ⁇ type metal, before the alkaline leaching. They may also be introduced as salts, which should advantageously be soluble, into the initial reaction medium but also as salts during the alkaline leaching of the alloy.
  • Said process is particularly well suited to substrates which have at least one nitrile function carried by an aliphatic ring, especially when said sxibstrate initially has an imine function carried by an aliphatic ring.
  • the method is particularly useful when said substrate is such that the final diamine has a cis/trans isomery with respect to a ring carrying the amine and aminomethyl functions (-CH 2 -NH 2 ) .
  • said hydrogenation step be stopped before the ratio corresponding to the cis/trans thermodynamic equilibrium is reached.
  • the imine and nitrile functions of the substrate are carried by an aliphatic isocyclic radical, wherein the nitrile function is carried by an intracyclic sp 3 hybridization carbon atom and the imine function carrying carbon atom is intracyclic and is linked to sp 3 hybridization carbon atoms .
  • the obtained results are of particular interest when the process is used for synthesizing cycloaliphatic amines, which are usually employed as the raw material for cycloaliphatic isocyanate (NBDI, H12MDI) and especially, for synthesizing IPDA.
  • the process according to the present invention leads to cis/trans ratios greater than 3 (which may range up to 5 or even about 15) .
  • a simple heating step allows this ratio to be reduced to the desired value (in general, about 3, as mentioned above).
  • the reaction time generally ranges from 1 hour to
  • the catalyst amount and hydrogen partial pressure are then chosen for the conversion rate to reach the chosen value after a time duration ranging from 1 hour to 10 hours.
  • iminated isophorone nitrile has the following formula:
  • One of the advantages of the present invention is to be able to dispense with the presence of a hydroxide (or any compound leading thereto in the reaction medium) , notably a monovalent metal or a quaternary ammonium- These hydroxides are objectionable according to the present invention.
  • the content of these compounds is more related to the impurity of the components of the reaction medium than to a possible intentional addition.
  • reaction mixture should contain at most 1%, advantageously at most I'ss and preferably 100 ppm in weight of such hydroxides, in particular alkaline metals .
  • Chromium + Nickel - 5% (analyzed 2.1% Cr and 2.4% Ni) Average Particle Size; 55 or 35 microns pH in water 11.5 (13 maximum)
  • the substrate was isophorone nitrile (IPN) ; the solvent was methanol; the internal standard was triethylene glycol dimethyl ether (triglyme) ; and the ammonia to substrate molar ratio was approximately 20.
  • IPN isophorone nitrile
  • the solvent was methanol
  • the internal standard was triethylene glycol dimethyl ether (triglyme)
  • the ammonia to substrate molar ratio was approximately 20.
  • IPIN Isophorone imine nitrile
  • Dry catalyst powders were added to arrays of 96 glass vials (1ml each) in common headspace parallel batch reactors for high-throughput testing (see European, Patent Application No. EP 1174185.
  • Stock solutions were added into vials (total amount 380mg ⁇ 5 mg) and the reactors were sealed before removing them from the glove box.
  • the reactors were placed in a vortex-heating unit and a gas line was attached that was evacuated and purged several times at 25°C before pressurizing with hydrogen (35 bar except if mentioned otherwise (one bar is 100 kPa) (500 psi) for these examples).
  • the vort ⁇ xing speed was increased to 800 rpm before the reactors were heated to the reaction temperature.
  • Example 2 ef ect of the potentiator elements introduced in the alloy precursor of the Raney® type cobalt
  • a 2700 or 2724 Cobalt catalyst from Grace Davison was used; the reaction temperature was 80°C.
  • the water content corresponds to the water formed by the ammonia ketone condensation.
  • the catalyst to substrate weight ratio the same in the two experiments. Without additives, the 2724 catalyst gave a higher yield and lower Cis/Trans ratio than the 2700 catalyst, 89.2% and 3.2 versus 85% and 3.5%.
  • Example 3 e ect of potentiator elements introduced through liquid phase on Raney® type cobalt with low nickel content
  • the reaction temperature was ⁇ 0°C.
  • the water content corresponds to the water formed by the ammonia 10 ketone condensation.
  • the catalyst to substrate weight ratio wasthe same in the experiments and the reaction time was 6 hours.
  • Trie amount of additive used (1.3 mole % of the active metal) was calculated by assuming that the
  • catalyst was pure cobalt and that only 10 wt. % was active as a catalyst.
  • Additives dissolved in methanol were added to the catalysts in vials that were agitated then allowed to stand overnight. The samples were then dried by gently blowing off the solvent with a stream of
  • the reaction temperature was 80 °C.
  • the water content corresponds to the water formed by the ammonia ketcne condensation.
  • the catalyst to substrate weight ratio was 0.13; and the reaction time was 6 hours.
  • the amount of additive used (1.3 mole % of the active metal) was calculated by assuming that the catalyst was pure cobalt and that only 10 wt- % was active as a catalyst.
  • Additives dissolved in methanol were added to the catalysts in vials that were agitated then allowed to stand overnight. The samples were then dried by gently blowing off the solvent with a stream of pure nitrogen gas inside a glove box. Palladium acetylacetonate slightly increased the IPDA yield of the 2724 catalyst.
  • the nickel is a bad potentiator
  • the platinum group metals are good potentiators.
  • the niobium, rhenium, titanium, vanadium and zinc are comparative .
  • IPDA Yield 87.0% (standard deviation 0.4) and Cis/Trans Ratio 4.3 (standard deviation 0.2).
  • reaction temperature 100°C, and for an average of 8 tests, the results read as follows:
  • Example 6 e ct of the Catalyst to Substrate Weight Ratio on the IPDA Yield and Cis/Trans ratio Two groups of experiment were tested.
  • the water content corresponds to the water formed by the ammonia ketone condensation.

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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)

Abstract

La présente invention concerne un procédé de synthétisation d'amines à partir de nitriles. Ce procédé est caractérisé en ce qu'il comporte une étape faisant intervenir un réactif contenant au moins- un catalyseur basé sur un métal du groupe VIII du tableau périodique des éléments, de l'eau et de l'ammoniaque. Ce procédé s'applique à la synthèse organique.
PCT/US2003/041441 2002-12-31 2003-12-31 Procede de synthetisation d'amines a partir de nitriles WO2004060866A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003302339A AU2003302339A1 (en) 2002-12-31 2003-12-31 Process for synthesizing amine from nitrile

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US43715502P 2002-12-31 2002-12-31
US60/437,155 2002-12-31

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WO2004060866A2 true WO2004060866A2 (fr) 2004-07-22
WO2004060866A3 WO2004060866A3 (fr) 2004-09-23

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010009995A2 (fr) 2008-07-25 2010-01-28 Basf Se 5-isopropyl-3-aminométhyl-2-méthyl-1-amino-cyclohexane (carvone diamine) et procédé de production de celui-ci

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0394967A1 (fr) * 1989-04-25 1990-10-31 Union Carbide Chemicals And Plastics Company, Inc. Amination réductive de carbonyl-nitriles et composés similaires
US6011179A (en) * 1997-10-30 2000-01-04 Degussa-Huls Ag Process for the production of amines from imines of nitriles
US6437186B1 (en) * 2000-12-23 2002-08-20 Degussa Ag Process for the preparation of 3-aminomethyl-3,5,5-trimethylcyclohexylamine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0394967A1 (fr) * 1989-04-25 1990-10-31 Union Carbide Chemicals And Plastics Company, Inc. Amination réductive de carbonyl-nitriles et composés similaires
US6011179A (en) * 1997-10-30 2000-01-04 Degussa-Huls Ag Process for the production of amines from imines of nitriles
US6437186B1 (en) * 2000-12-23 2002-08-20 Degussa Ag Process for the preparation of 3-aminomethyl-3,5,5-trimethylcyclohexylamine

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010009995A2 (fr) 2008-07-25 2010-01-28 Basf Se 5-isopropyl-3-aminométhyl-2-méthyl-1-amino-cyclohexane (carvone diamine) et procédé de production de celui-ci
WO2010009995A3 (fr) * 2008-07-25 2010-04-01 Basf Se 5-isopropyl-3-aminométhyl-2-méthyl-1-amino-cyclohexane (carvone diamine) et procédé de production de celui-ci
US8586794B2 (en) 2008-07-25 2013-11-19 Basf Se 5-isopropyl-3-aminomethyl-2-methyl-1-amino-cyclohexane (carvone diamine), and method for the production thereof

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WO2004060866A3 (fr) 2004-09-23
AU2003302339A8 (en) 2004-07-29

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