WO2008130721A1 - Préparation de diamines secondaires - Google Patents

Préparation de diamines secondaires Download PDF

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Publication number
WO2008130721A1
WO2008130721A1 PCT/US2008/050664 US2008050664W WO2008130721A1 WO 2008130721 A1 WO2008130721 A1 WO 2008130721A1 US 2008050664 W US2008050664 W US 2008050664W WO 2008130721 A1 WO2008130721 A1 WO 2008130721A1
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WIPO (PCT)
Prior art keywords
ketone
diamine
aliphatic
aldehyde
carbon
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PCT/US2008/050664
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English (en)
Inventor
John Y. Lee
Paul L. Wiggins
Richard D. Glass
Judit Orgad
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Albemarle Corporation
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Publication of WO2008130721A1 publication Critical patent/WO2008130721A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
    • C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
    • 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
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/14—Amines containing amino groups bound to at least two aminoalkyl groups, e.g. diethylenetriamines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • This invention relates to the preparation of secondary diamines from primary diamines.
  • Imines are often formed from combination of a primary amine and an aldehyde or ketone. Such imines can be used as flavors (see U.S. 3,625,710) or fragrances (see EP 1067116).
  • chain extenders with slower cure rates, so it is desirable to have diamines that exhibit slower curing rates. It is thus further desirable to have routes to secondary diamines, especially when such processes are conducted under mild conditions. It would also be desirable to produce chain extenders having low amounts of impurities that do not function as chain extenders.
  • This invention provides processes for preparing aliphatic secondary diamines under mild conditions.
  • An advantage of the relatively mild pressure and temperature conditions used in the processes of the invention is that ordinary process apparatus can be employed, so there is no need for specialized equipment, such as that required for high-pressure reactions.
  • Another advantage of the processes of this invention is that the production of tertiary amines, which do not function as chain extenders, is minimized. While the processes of this invention do produce small amounts of coupling product secondary diamines (in which the ketones adding to at least one of the amino groups have coupled), these coupling product secondary diamines do function as chain extenders, unlike tertiary amines.
  • An embodiment of this invention is a process for forming a secondary diamine.
  • the process comprises bringing together a) at least one aliphatic hydrocarbyl ketone or aldehyde in which the carbon atom(s) alpha to the carbonyl group are primary or secondary and the hydrocarbyl portion of the ketone or aldehyde is linear or branched; b) at least one aliphatic primary diamine which is an aliphatic primary ⁇ , ⁇ -diamine, c) hydrogen; and d) a hydrogenation catalyst selected from platinum on carbon, palladium on carbon, sulfided platinum on carbon, sulfided palladium on carbon, and a mixture of any two of the foregoing.
  • the process is conducted at a temperature in the range of about 20 ° C to about 76 ° C and at a hydrogen pressure in the range of about 1 to about 85 pounds per square inch gauge (1.08x10 5 to
  • Another embodiment of this invention is an aliphatic secondary triamine composition represented by the formula
  • R and R are each, independently, aliphatic hydrocarbyl groups which are linear or branched, and R and R are each, independently, aliphatic straight chain hydro carbylene groups.
  • Diimines that are products of a reaction of a primary diamine and a carbonyl compound are sometimes called Schiff bases, and such diimines are formed by at least some of the processes of the invention.
  • the carbonyl compound used to form the diimine is a ketone
  • such a diimine is occasionally referred to as a ketimine or diketimine.
  • the formation of a secondary diamine from a primary diamine and a ketone is often referred to as reductive alkylation or reductive amination, and the terms "reductive alkylation” and "reductive animation” can be used to describe the processes of this invention.
  • psig pounds per square inch gauge
  • tertiary diamine refers to a diamine in which one or both of the amino groups is tertiary. The presence of a tertiary amino group renders the molecule unable to function as a chain extender.
  • aliphatic secondary diamines are prepared in one step via the bringing together of a ketone or aldehyde, an aliphatic primary diamine, hydrogen, and a hydrogenation catalyst.
  • the ketone is at least one aliphatic hydrocarbyl ketone in which the carbon atom(s) alpha to the carbonyl group are primary or secondary and the hydrocarbyl portion of the ketone or aldehyde is linear or branched
  • the aldehyde is at least one aliphatic hydrocarbyl aldehyde in which the carbon atom(s) alpha to the carbonyl group are primary or secondary and the hydrocarbyl portion of the ketone or aldehyde is linear or branched
  • the aliphatic primary diamine is at least one aliphatic primary diamine which is an aliphatic primary ⁇ , ⁇ -diamine
  • the hydrogenation catalyst is selected from platinum on carbon, palladium on carbon, and a mixture thereof.
  • the process is conducted at a temperature in the range of about 20° C to about 76° C and at a hydrogen pressure in the range of about 1 to about 85 pounds per square inch gauge (1.08xl0 5 to 6.87xlO 5 Pa).
  • the ketones and aldehydes used in the processes of this invention are aliphatic hydrocarbyl ketones and aliphatic hydrocarbyl aldehydes in which the carbon atom(s) alpha to the carbonyl group are primary or secondary.
  • the hydrocarbyl portion of the ketone or aldehyde is linear or branched.
  • the ketones and aldehydes used in the practice of this invention have from three to about twenty carbon atoms.
  • ketones and aldehydes having from three to about fifteen carbon atoms.
  • ketones and aldehydes have an alkyl portion which is a branched alkyl group, and have from three to about ten carbon atoms.
  • Suitable monoketones include acetone (2-propanone), methyl ethyl ketone (2-butanone), 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 4-heptanone, 3-octanone, A- octanone, 3-nonanone, 5-nonanone, 2-undecanone, 6-undecanone, di-n-hexyl ketone, 8- pentadecanone, 9-heptadecanone, 10-nonadecanone, 3-methyl-2-pentanone, 3-methyl-2- butanone (methyl isopropyl ketone), 4-methyl-2-pentanone (methyl isobutyl ketone), 3,3- dimethyl-2-butanone (methyl tert-butyl ketone), 5-methyl-2-hexanone, 4-methyl-3-heptanone, 2,4-dimethyl-3-pentanone, 2,6-di
  • Preferred monoketones include acetone, methyl ethyl ketone, and A- methyl-2-pentanone.
  • Acetone is a more preferred monoketone in the practice of this invention.
  • Examples of diketones that can be used in the practice of this invention include tetramethyl-l,3-cyclobutanedione, 1,3-cyclopentanedione, 1,3-cyclohexanedione, 2-methyl-l,3- cyclopentanedione, 1 ,4-cyclohexanedione, 1 ,3-cycloheptanedione, 1 ,4-cycloheptanedione, 5- methyl- 1,3-cyclohexanedione, 4,4-dimethyl- 1,3-cyclohexanedione, 5-isopropyl-l,3- cyclohexanedione, bicyclo[3.3.1]nonane-3,7-d
  • Monoaldehydes that can be used in the practice of this invention include acetaldehyde, propionaldehyde, butyr aldehyde, valeraldehyde (pentanal), isovaleraldehyde, hexanal, heptaldehyde, octyl aldehyde, nonyl aldehyde, decyl aldehyde, undecyl aldehyde, dodecyl aldehyde, 2-ethylbutyraldehyde, undecylenic aldehyde (10-undecenal), and the like.
  • dialdehydes or polyaldehydes can be employed.
  • dialdehydes that can be used in the practice of this invention include glyoxal, succinaldehyde, ethyl succinaldehyde, glutaraldehyde, 2-methylglutaraldehyde, 3- methylglutaraldehyde, adipaldehyde, and the like.
  • the use of one or more dialdehydes or polyaldehydes may yield oligomeric or polymeric products.
  • mixtures may be employed. Such mixtures can include two or more ketones, two or more aldehydes, or at least one ketone and at least one aldehyde. The use of a mixture of ketones and/or aldehydes may result in a mixture of products.
  • Diketones and/or polyketones can be used in lieu of or in addition to monoketones.
  • Suitable diketones and polyketones include, but are not limited to, 2,3-butanedione, 2,4- pentanedione (acetylacetone), 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, 2,4- hexanedione, 2,5-hexanedione (acetonylacetone), 2,5-heptanedione, 6-methyl-2,4-heptanedione, 3,5-heptanedione, methine triacetate, diacetylacetone (2,4,6-heptanetrione), 3-acetyl-2,5- hexanedione, and 3-acetyl-2,6-heptanedione.
  • the use of one or more diketones may yield oligomeric or polymeric products.
  • the ketone and/or aldehyde is in liquid form when used in the processes of the invention.
  • elevated temperatures and/or increased pressure will liquefy the ketone or aldehyde.
  • a solvent may be used to provide the ketone or aldehyde in liquid form.
  • the aliphatic primary diamines used in the processes of this invention are aliphatic primary ⁇ , ⁇ -diamines.
  • the aliphatic primary ⁇ , ⁇ -diamines are primary diamines which are in the form of a straight chain, with a primary amino group bound to each of the two terminal carbon atoms.
  • the straight chain is either a hydrocarbyl straight chain or a secondary amino straight chain, where "secondary amino straight chain” means a straight chain in which at least one of the -CH 2 - moieties in a hydrocarbyl straight chain is instead an -NH- moiety.
  • Such internal secondary amino groups of the aliphatic primary diamine do not become tertiary in the processes of this invention.
  • the aliphatic primary ⁇ , ⁇ -diamine has about three to about twenty carbon atoms; more preferably, the aliphatic primary ⁇ , ⁇ -diamine has about four to about ten carbon atoms.
  • aliphatic primary diamines with at least one internal secondary amino group are preferred, because the secondary diamines formed therefrom are able to provide crosslinking when employed as chain extenders.
  • Suitable aliphatic primary diamines include, but are not limited to, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1 ,6-diaminohexane, 1,7-diaminoheptane, 1,8- diaminooctane, 1 , 10-diaminodecane, 1,12-diaminododecane, diethylenetriamine (N-(2- aminoethyl)-l,2-ethanediamine), norspermidine, spermidine, bis(hexamethylene)triamine, N-(3- aminopropyl)cadaverine, N-(3-aminopropyl)-l,7-heptanediamine, triethylenetetramine, and tetraethylenepentamine.
  • Preferred aliphatic primary diamines include 1 ,6-diaminohexane, bis(hexamethylene)triamine, and diethylenetriamine.
  • Preferred combinations in the processes of this invention include the use of 1,6-diaminohexane with acetone, the use of 1 ,6-diaminohexane with methyl isobutyl ketone, and the use of diethylenetriamine with acetone.
  • the aliphatic primary diamine is in liquid form when it is used in the processes of the invention. For some primary diamines, elevated temperatures and/or increased pressure will liquefy the primary diamine. If such conditions are not used, a larger amount of ketone or a solvent may be used to provide the primary diamine in liquid form.
  • the mole ratio of ketone or aldehyde to aliphatic primary diamine is normally at least about one mole of ketone or aldehyde per mole of amino group, i.e., at least about two moles of monoketone or monoaldehyde per mole of diamine.
  • an excess of the ketone or aldehyde is used, preferably at least about a 10% molar excess of ketone or aldehyde relative to the primary diamine is used.
  • Mole ratios of monoketone or monoaldehyde to aliphatic primary diamine in the range of about 2.2:1 to about 10:1 are effective, and thus are preferred; more preferred are mole ratios of monoketone or monoaldehyde to aliphatic primary diamine in the range of about 2.5: 1 to about 6:1.
  • Large excesses of ketone or aldehyde are acceptable in the practice of the invention; the ketone or aldehyde can be, and for monoketones and monoaldehydes preferably is, present in enough quantity to also act as a solvent.
  • ketone or aldehyde is often considered beneficial because, as is well known in the art, the formation of a diimine (which is believed to be an intermediate in the formation of the secondary diamines in the processes of this invention) behaves as an equilibrium, and excess ketone or aldehyde shifts the equilibrium to favor diimine formation.
  • the mole ratio of ketone or aldehyde to aliphatic primary diamine is normally at least about one mole of ketone group per mole of amino group, i.e., at least about one mole of diketone or dialdehyde per mole of diamine.
  • an excess of the ketone or aldehyde is used, preferably at least about a 10% molar excess of ketone or aldehyde relative to the primary diamine is used.
  • Mole ratios of diketone or dialdehyde to aliphatic primary diamine in the range of about 1.1 :1 to about 5:1 are effective, and thus are preferred; more preferred are mole ratios of diketone or dialdehyde to aliphatic primary diamine in the range of about 1.2:1 to about 3:1. These ratios can be adjusted as necessary for polyketones or poly aldehydes, e.g., for triketones or trialdehydes.
  • a diketone, polyketone, dialdehyde, or polyaldehyde can be present in enough quantity to also act as a solvent.
  • the hydrogenation catalyst used in this invention is platinum on carbon, palladium on carbon, sulfided platinum on carbon, sulfided palladium on carbon, or a mixture of any two of the foregoing. Use of one type of catalyst rather than a mixture of catalysts is preferred.
  • Platinum on carbon and palladium on carbon are preferred hydrogenation catalysts in the practice of this invention, with platinum on carbon being more preferred.
  • platinum on carbon or palladium on carbon When platinum on carbon or palladium on carbon is used, it can be in either powdered form or in granular form. While the presence of a strong acid with platinum on carbon or palladium on carbon is generally unnecessary, it may be desirable to rinse the catalyst with an acid prior to use, or to have an acid present during the process.
  • Suitable acids include a strong acid such as sulfuric acid, hydrochloric acid, phosphoric acid, and the like, or a carboxylic acid such as formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, and the like. Strong acids are usually used as aqueous solutions of the acid. When an acid will be present during the process, it should be remembered that strong acids can cause dimerization and/or polymerization of some ketones.
  • Suitable amounts of hydrogenation catalyst can be relatively low, i.e., in the range of about 1 wt% to about 10 wt% relative to the primary diamine. More suitably, in the range of about 3 wt% to about 5 wt% hydrogenation catalyst can be used relative to the primary diamine.
  • hydrogenation catalyst can be relatively low, i.e., in the range of about 1 wt% to about 10 wt% relative to the primary diamine. More suitably, in the range of about 3 wt% to about 5 wt% hydrogenation catalyst can be used relative to the primary diamine.
  • water removal agent may be included in the reaction mixture to remove water as the water is produced in the process. The only requirement is that the water removal agent not adversely affect the reaction or its products. Suitable water removal agents include molecular sieves, silica gel, calcium chloride, and the like. Molecular sieves are a preferred water removal agent in the practice of this invention.
  • a recommended and preferred alternative to the use of a water removal agent is the inclusion of a solvent or enough excess ketone or aldehyde to act as the solvent to effectively dilute the water is recommended and preferred.
  • a solvent that is able to azeotrope with water and thereby remove water as it is produced during a process is a preferred way of operating.
  • Preferred solvents that remove water are hexanes and toluene.
  • Another preferred way of operating when using a solvent is to use a solvent which takes water into a phase separate from that in which the reaction is occurring; preferred solvents for this way of operating include toluene and dichloromethane.
  • Both inclusion of a solvent or enough excess ketone or aldehyde to act as the solvent and the use of a water removal agent may be employed to minimize the amount of water.
  • An especially preferred way of operating is to employ enough excess ketone or aldehyde to dilute the water.
  • water is not present as an ingredient in the processes of the invention at the start of the process, except for adventitiously present water (e.g., less than about 1 wt% water relative to the total weight of the reaction mass).
  • adventitiously present water e.g., less than about 1 wt% water relative to the total weight of the reaction mass.
  • solvent types that can be used in the processes of this invention include, but are not limited to, liquid aromatic hydrocarbons, liquid aliphatic hydrocarbons, liquid halogenated aliphatic hydrocarbons, liquid halogenated aromatic hydrocarbons, ethers, esters, alcohols, and a mixture of two or more solvents.
  • an alcohol especially a C 1-4 alcohol, is present during the process.
  • Such an alcohol is typically about 25 wt% to about 75 wt% of the total weight of the reaction mixture; preferably, the alcohol is 45 wt% to about 65 wt% of the total weight of the reaction mixture.
  • carboxylic acid may be desirable.
  • Carboxylic acids that can be used in the practice of this invention include formic acid, acetic acid, and propionic acid. As mentioned above, when an acid will be present during the process, it should be remembered that strong acids can cause dimerization and/or polymerization of some ketones.
  • Suitable liquid hydrocarbons include benzene, toluene, xylenes, mesitylene, cumene, cymene, pentane, hexane, isohexane, cyclohexane, methylcyclohexane, heptane, octane, cyclooctane, nonane, and the like.
  • liquid halogenated aliphatic hydrocarbons examples include dichloromethane, trichloro methane, 1 ,2-dichloroethane, l-bromo-2- chloroethane, (chloromethyl) cyclopropane, 1-bromobutane, cyclobutyl chloride, neopentyl chloride, l-bromo-5-chloropentane, cyclopentyl bromide, 1,6-dibromohexane, trans-1,2- dichlorocyclohexane, 1-chloroheptane, 1,8-dichlorooctane, and the like.
  • Ethers that are suitable for use in this invention include diethyl ether, di- «-propyl ether, diisopropyl ether, di- «-butyl ether, butyl ethyl ether, cyclohexylmethyl ether, tetrahydrofuran, 1,3-dioxane, 1,3-dioxolane, glyme (the dimethyl ether of ethylene glycol), 2-methoxyethyl ether (diglyme), and the like.
  • Suitable liquid halogenated aromatic hydrocarbons include chlorobenzene.
  • esters examples include ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert- butyl acetate, n-amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, and the like.
  • Alcohols including C1-4 alcohols, that can be used in the practice of the invention include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-l- propanol, 1 -methyl- 1-propanol, cyclopropylmethanol, cyclobutanol, cyclopentanol, cis-2- methylcyclohexanol, and the like.
  • Preferred solvents include dichloromethane, ethyl acetate, toluene, and especially methanol and/or ethanol.
  • the processes of the invention are conducted at a temperature in the range of about 20° C to about 76° C and at a hydrogen pressure in the range of about 1 to about 85 pounds per square inch gauge (1.08xl0 5 to 6.87xlO 5 Pa).
  • temperatures are in the range of about 40°C to about 76° C, and pressures are preferably in the range of about 50 to about 76 pounds per square inch gauge (4.46x10 5 to 6.25x10 5 Pa).
  • the ketone, primary diamine, catalyst, and hydrogen may be brought together in any order. It is believed that the hydrogenation catalyst is necessary to obtain the secondary diamine in better yield and/or in shorter periods of time.
  • a particularly preferred method for preparing a secondary diamine is to place the primary diamine, hydrogenation catalyst, and solvent in a reaction vessel, and then to seal the reaction vessel under hydrogen gas pressure. The vessel is then heated as desired while the reaction mixture is stirred. On the laboratory scale, reaction times are typically about six hours to about fifteen hours.
  • this process has yielded predominately secondary diamines.
  • Tertiary diamines when observed, have been seen in amounts of about 1% or less, often in amounts of about 0.5% or less, and in amounts of about 0.3% or less, where the percentage is a gas chromatograph (GC) area percent of an unpurified product mixture produced by the processes of this invention.
  • GC gas chromatograph
  • unpurified product mixture refers to the secondary aliphatic diamine in admixture with co-products and/or impurities resulting from preparation by bringing together an aliphatic cyclic ketone, an aliphatic primary diamine, hydrogen, and a hydrogenation catalyst selected from platinum on carbon, palladium on carbon, and a mixture thereof.
  • the composition of the product is process-determined and not the result of use of downstream purification techniques, such as recrystallization, chromatography, distillation, or like procedures that can affect the chemical composition of the product mixture.
  • the secondary diamines produced by the processes of this invention are usually liquids.
  • Methods for separating liquids that are well known in the art can be employed to separate at least a portion of the diamine from the other components of the reaction mixture. Such methods include, for example, recrystallization, chromatography and distillation. Distillation is a preferred separation method.
  • standard solid- liquid separation methods such as centrifugation, filtration, or recrystallization can be used to separate at least a portion of the product from the liquid portion of the reaction mixture. If desired, the secondary diamines can be used in non-isolated form.
  • Separation of the ketone from the reaction mixture can be performed by distillation, with separation of aqueous portions of any azeotropes encountered, or with decantation of the aqueous layer followed by distillation of the ketone layer. Once at least a portion of the product diimine or secondary diamine has been removed from the reaction mixture, unreacted starting materials can be recycled to the reactor to form a portion of the feed stock.
  • Products of the processes of this invention are aliphatic secondary diamines which include, but are not limited to, N,N'-diisopropylethylenediamine, N,N'-di(5-nonyl)-l,3- diaminopropane, N,N'-di(3-methyl-2-butyl)-l,4-diaminobutane, N,N'-di(l-pentyl)-l,5- diaminopentane, N,N'-diisopropyl- 1 ,6-diaminohexane, N,N'-di-sec-butyl- 1 ,6-diaminohexane, N,N'-di(l-hexyl)-l,6-diaminohexane, N,N'-diisopropyl-l,7-diaminoheptane, N,N'-di(
  • compositions of this invention are aliphatic secondary triamines represented by the formula R'-NH-R ⁇ NH-R ⁇ NH-R 2 in which R and R are each, independently, aliphatic hydrocarbyl groups which are linear or branched, and R and R are each, independently, aliphatic straight chain hydrocarbylene groups.
  • R and R can be the same or different; typically, they will be different if a mixture of ketones and/or aldehydes is used.
  • R 1 and R 2 can be primary, secondary, or tertiary hydrocarbyl groups which are linear or branched.
  • R 1 and R 2 have from three to about twenty carbon atoms; more preferably, R 1 and R 2 have from three to about fifteen carbon atoms.
  • Especially preferred groups R 1 and R 2 are branched alkyl groups, and have from three to about ten carbon atoms.
  • Preferred as R 1 and R 2 are isopropyl groups, sec-butyl groups, and 4-methyl-2-pentyl groups.
  • R 3 and R 4 will be different when the number of carbon atoms in their respective hydro carbylene groups is different.
  • R 3 and R 4 preferably have about three to about twenty carbon atoms; more preferably, R and R have about four to about ten carbon atoms.
  • Aliphatic secondary triamine compositions of this invention include N,N'-diisopropyl-diethylenetriamine.
  • Example 2 was repeated, except that the hydrogen pressure was 85 psig (6.87xlO 5 Pa), and the heating at 70°C was for 12 hours.
  • GC showed a greater than 97% yield of N,N'- diisopropyl- 1,6-diaminohexane, approximately 2% of over-alkylated byproducts, and 0.3% of tertiary diamine.
  • reactants and components referred to by chemical name or formula anywhere in this document, whether referred to in the singular or plural, are identified as they exist prior to coming into contact with another substance referred to by chemical name or chemical type ⁇ e.g., another reactant, a solvent, or etc.). It matters not what preliminary chemical changes, transformations and/or reactions, if any, take place in the resulting mixture or solution or reaction medium as such changes, transformations and/or reactions are the natural result of bringing the specified reactants and/or components together under the conditions called for pursuant to this disclosure.
  • the reactants and components are identified as ingredients to be brought together in connection with performing a desired chemical operation or reaction or in forming a mixture to be used in conducting a desired operation or reaction.
  • an embodiment may refer to substances, components and/or ingredients in the present tense ("is comprised of, “comprises”, “is”, etc.), the reference is to the substance, component or ingredient as it existed at the time just before it was first contacted, blended or mixed with one or more other substances, components and/or ingredients in accordance with the present disclosure.

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Abstract

L'invention concerne un procédé de formation de diamines secondaires. Le procédé comprend le rassemblement a) d'au moins une hydrocarbyl cétone ou un hydrocarbyl aldéhyde aliphatique dans lequel le ou les atomes de carbone alpha par rapport au groupe carbonyle sont primaires ou secondaires et la portion hydrocarbyle de la cétone ou de l'aldéhyde est linéaire ou ramifiée ; b) d'au moins une diamine primaire aliphatique qui est une α,ω-diamine primaire aliphatique, c) de l'hydrogène ; et d) d'un catalyseur d'hydrogénation choisi parmi platine sur carbone, palladium sur carbone, platine sulfuré sur carbone, palladium sulfuré sur carbone et un mélange de deux quelconque d'entre eux. Le procédé est conduit à une température se situant dans une plage d'environ 20 °C à environ 76 °C et à une pression d'hydrogène se situant dans une plage d'environ 1 à environ 85 livres par pouce carré relative, de sorte qu'une diamine secondaire est formée.
PCT/US2008/050664 2007-04-19 2008-01-09 Préparation de diamines secondaires WO2008130721A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
WO2017060827A1 (fr) * 2015-10-07 2017-04-13 Lupin Limited Procédé amélioré pour la préparation de sélexipag ou de ses sels pharmaceutiquement acceptables
CN111909039A (zh) * 2020-09-07 2020-11-10 江苏湘园化工有限公司 一种高位阻效应的脂肪族二元仲胺的制备方法

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