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WO2017105985A1 - Préparation d'isohexide-3,6-dicarbaldéhydes et d'isohexide-3,6-diméthanamines - Google Patents

Préparation d'isohexide-3,6-dicarbaldéhydes et d'isohexide-3,6-diméthanamines Download PDF

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Publication number
WO2017105985A1
WO2017105985A1 PCT/US2016/065521 US2016065521W WO2017105985A1 WO 2017105985 A1 WO2017105985 A1 WO 2017105985A1 US 2016065521 W US2016065521 W US 2016065521W WO 2017105985 A1 WO2017105985 A1 WO 2017105985A1
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Prior art keywords
isohexide
dicarbaldehyde
hexahydrofuro
furan
dimethanamine
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English (en)
Inventor
Kenneth STENSRUD
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Archer Daniels Midland Co
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Archer Daniels Midland Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems

Definitions

  • the present disclosure relates to certain cyclic bifunctional monomers derived from renewable materials.
  • the present invention pertains to methods for the synthesis of dicarbaldehydes and corresponding methanamines from the dehydration products of sugar alcohols.
  • Biomass contains carbohydrates or sugars that can be converted into value added products.
  • Carbohydrates suffer from discrete shortcomings. In contrast to petroleum-based hydrocarbon molecules, which contain limited or lesser amounts of functional groups, carbohydrates such as polysaccharides are markedly complex, over-functionalized hydrophilic materials. Carbohydrates contain many -OH functionality which limits interactive capacities in, for example, non-aqueous media, as well as exhibit a tendency to degrade under traditional high temperature processes.
  • biomass-derived chemicals that are prepared solely from carbohydrates, but which are less highly functionalized, including more stable bi-functional compounds, such as 2,5-furandicarboxylic acid (FDCA), levulinic acid, and 1,4:3,6- dianhydrohexitols.
  • FDCA 2,5-furandicarboxylic acid
  • levulinic acid levulinic acid
  • 1,4:3,6- dianhydrohexitols 1,4:3,6- dianhydrohexitols.
  • 1,4:3, 6-Dianhydrohexitols are molecular species thai embody a class of bicyclic tetrahydrofuranodiols, which are prepared from corresponding reduced sugar alcohols (D-sorbitol, D-mannitol, and D-iditol respectively).
  • D-sorbitol, D-mannitol, and D-iditol are prepared from corresponding reduced sugar alcohols
  • D-sorbitol, D-mannitol, and D-iditol reduced sugar alcohols
  • three isomers of the isohexides exist, namely: A) isomannide, B) isosorbide, and C) isoidide, respectively; the structures of which are illustrated in Scheme A.
  • Scheme A Structures of isomannide A, isosorbide B, and isoidide C.
  • the present disclosure describes, in part, a straightforward method for making either isohexide-3,6-dicarbaldehydes or 3,6-dimethanamines.
  • the method involves transforming, initially, an isohexide into an isohexide-3,6-dinitrile, then providing a reaction mixture containing isohexide-3,6-dinitriles and an anhydrous, inert, organic solvent, contacting the isohexide-3,6- dinitriles with a reducing agent at a reaction temperature for a time sufficient to produce the isohexide-3,6-dicarbaldehyde.
  • the method may further involve contacting the isohexide-3,6- dicarbaldehyde with an aminating agent under a reducing condition to generate isohexide-3,6- dimethanamines.
  • the disclosure pertains to a method of preparing an isohexide derivative compound of an isohexide-3,6-dicarbaldehyde.
  • the method involves reacting a mixture containing isohexide-3,6-dinitriles, and an inert organic solvent and a reducing agent at a reaction temperature between about -50°C to about -100°C, forming an isohexide-3,6-dicarbaldehyde, and then transforming the isohexide-3,6-dicarbaldehyde into a dimethanimine or dimethanamine.
  • the method may be further adapted to prepare a derivative compound of an isohexide-3,6-dimethanamine, after reductive amination of the isohexide-3,6-dicarbaldehyde. For instance, amidating the isohexide-3,6-dimethanamine to generate a poly amide.
  • the present invention describes, in part, an efficient and simple process for synthesizing isohexide-3,6-dicarbaldehydes and isohexide-3,6-dimethanamines from l,4:3,6-dianhydrohexitols (referred to as "isohexides” in the Description hereinafter).
  • isohexides l,4:3,6-dianhydrohexitols
  • Each of these types of molecules can serve as valuable chemical substrates or precursor molecules in the preparation of a variety of potential chemical compounds, including for instance, chiral auxiliaries (asymmetic synthesis used in pharmaceutical production), surfactants, solvents, acrylics and other polymeric materials.
  • Scheme 1 presents an illustration of the present synthesis method according to an embodiment to make an isohexide-3,6- dicarbaldehyde, and then isohexide-3,6-dimethanamine.
  • an isohexide (A) is first transformed into its corresponding isohexide-3,6-dinitrile (C).
  • the isohexide can be any one of the sugar alcohols - isomannide, isosorbide, or isoidide.
  • the process is initiated by a triflate nucleofugation of the -OH moieties of the isohexide.
  • An isohexide and triflic anhydride are reacted in a pyridine-rich matrix forming an isohexide di-triflate (B), followed by a carbon-centered nitrile-for-triflate substitution, underscored by a Walden inversion.
  • the synthesis involves providing a reaction mixture containing the isohexide-3,6-dinitrile and an anhydrous, inert, organic solvent, and reacting the isohexide-3,6- dinitrile (C) with a reducing agent at a reaction temperature for a time sufficient to produce the isohexide-3,6-dicarbaldehyde (D).
  • Scheme 2 presents the structures of the corresponding resultant isohexide-3,6-dicarbaldehyde for isomannide, isosorbide, and isoidide starting materials: isomannide-3,6-dicarbaldehyde 1, isosorbide-3,6-dicarbaldehyde 2, and isoidide-3,6-dicarbaldehyde 3.
  • Scheme 3 shows the corresponding structures of isomannide-3,6-dimethanamine A, isosorbide-3,6-dimethanamine B, and isoidide-3,6-dimethanamine C
  • the present process is able to produce primarily isohexide-3,6-dicarbaldehydes in reasonably high yields of at least 47 mol.% from the isohexide-3,6-dinitrile starting materials and subsequently the isohexide-3,6-dimethanamines in yields of at least 68 mol.% from the isohexide-3,6- dicarbaldehydes.
  • the yield of isohexide-3,6-dicarbaldehyde is in a range from about 50 mol.% or 55 mol.% to about 75 mol.% or 80 mol.% (e.g., 57%, 60%, 63%, 65%, 68%, 70%, 72%, 78%); with optimization of the process the yield can achieve about 85 mol.% to 90 mol.% or 93 mol.% or greater.
  • the yield of the isohexide-3,6-dimethanamine is in a range from about 70 mol.% or 75 mol.% to about 85 mol.% or 95 mol.% (e.g., 72%, 78%, 80%, 83%, 88%, 90%, 92%).
  • the initial reductive step involves reaction of an isohexide-3,6-dinitrile and a sterically-hindered metal hydride in an inert solvent at a temperature from about -70°C to about -80°C, followed by an aqueous workup to quench excess hydride.
  • the resultant isohexide-3,6-dicarbaldehydes are then iminated with benzylamine at a temperature from about -5°C to -20°C in absolute ethanol, followed by catalytic hydrogenation in the unperturbed matrix, to generate the isohexide-3,6-dimethanamines.
  • the reducing agent is diisobutylaluminium hydride (DIBALH).
  • DIBAL-H diisobutylaluminium hydride
  • Some other metal hydrides may include, for example, sodium borohydride and lithium aluminum hydride.
  • DIBAL-H one benefits from a very low temperature (about -78°C) to preclude imine reduction before hydrolysis.
  • reducing agents that can be used in this transformation are heterogeneous catalysts, such as Raney nickel or sponge copper.
  • the reduction reaction should be performed at an extremely low temperatures that range from about -50°C to about -100°C. Typically, the temperature range is from about -55°C or -60°C to about -85°C or -90°C, more typically the range is from about -65°C to about -80°C (e.g., -70°C, -75°C, or - 78°C). Such low temperatures help to moderate the reaction.
  • the kinetics of the process enables the dialdehydes to be isolated at low temperatures; elevated temperatures result in the abrupt reduction of imine intermediates before hydrolysis can occur, generating the thermodynamically favored diamines.
  • the inert organic solvent is a polar and aprotic solvent species.
  • Some solvents can have a melting point below -90°C; such organic solvents may include tetrahydrofuran (THF), methylene chloride, or diethyl ether.
  • THF tetrahydrofuran
  • methylene chloride methylene chloride
  • diethyl ether diethyl ether
  • the solvents may include, for example, dimethylformamide (DMF), dimethylacetamide (DMA), 1,4-dioxane, or toluene.
  • benzylamine (BnN3 ⁇ 4) is a favored reactant as it is stable and a facile primary amine precursor.
  • the benzyl group is removed easily by hydrogenation under mild conditions.
  • Other reagents that can generate amines may include aqueous ammonia or ammonium chloride ammonia. Ammonia is less favored to use, however, owing to its corrosiveness.
  • Amination can be performed under ambient temperatures in a range from about 10°C to about 50°C (e.g., 12°C, 15°C, 18°C, 20°C, 22°C, 25°C, 30°C, 32°C, 35°C, 40°C, or 45°C).
  • benzylamine reduction to primary amine one may employ ethanol as the solvent, but methanol, ethyl acetate, THF, DMF, dimethyl sulfoxide (DMSO) can also be used. Alternatively, one may also use heterogeneous catalysts such as Ru/C, Pt/C, Pd/C, and Raney Ni with H 2 gas to reduce benzylamine to primary amines.
  • the isohexide-3,6-dicarbaldehydes and isohexide- 3,6-dimethanamines can be modified to generate functionalized materials that can be useful as precursors for making other chemical compounds, such as polymers, lubricants, surfactants, additives, and dispersants.
  • a method of preparing an isohexide derivative compound involves: reacting a solution containing isohexide-3,6-dinitriles, and an inert organic solvent with a (sterically-hindered) reducing agent at a reaction temperature between about -50°C to about -100°C; forming an isohexide-3,6-dicarbaldehyde; and transforming said isohexide-3,6-dicarbaldehyde into other bicyclic tetrahydrofuranic derivative compounds.
  • the transformation may entail performing either 1) a reductive animation and polymerization, or 2) a bis-allylation and glycolation on the isohexide-3,6-dicarbaldehyde.
  • the isohexide-3,6-dicarbaldehyde is reacted with a dialkyl amine (e.g., dibutylamine in the paradigm shown in Scheme 5, below) at room temperature, generating a polyimine precursor, which is then hydrogenated under mild conditions, effectively reducing the imine moieties to the corresponding amine.
  • a dialkyl amine e.g., dibutylamine in the paradigm shown in Scheme 5, below
  • Grignard reagents are used.
  • a favored and feasible route to produce diallyl analogs is to deploy allyl magnesium bromide as the Grignard reagent, reacting with a stoichiometric amount of dialdehyde at a temperature in the range from about -65°C to about -85°C (e.g., -75°C, -78°C, -80°C) then quenching the reaction with water.
  • allyl magnesium bromide is used in a typical embodiment.
  • Other potential Grignard reagents can include allyl magnesium chloride and allyl magnesium iodide.
  • the resulting isohexide-3,6-dicarbaldehyde derivative compound respectively from each reaction can be either a) diaminohexane -isohexide or diiminohexane-isohexide polymer or b) diallyl-glycols.
  • Scheme 4 Al), A2) and B) respectively depict the general structure of each of these compounds.
  • Scheme 5 shows an example of a particular compound formed of the polymerization of isohexide-3,6-di-dicarbaldehyde and dibutylamine.
  • isohexide-3,6-dicarbaldehyde derivative compounds may include at least one of the following:
  • Scheme 6 shows the general structure of an isohexide-3,6-diamine-terephthalate polyamide.
  • Examples of some particular terephthalic-isohexide amine polymers may include at least one of the following:
  • Example 1 Synthesis of (3 R,3aS,6S,6aS)-hexahydrofuro[3,2-b]furan-3, 6-diyl bis- (trifluoromethane-sulfonate), B.
  • Example 3 Synthesis of (3R,3aR,6S,6aR)-hexahydrofuro[3,2-b]furan-3,6-dicarbaldehyde, D.
  • Example 3 Synthesis of (3S,3aR,6S,6aR)-hexahydrofuro[3,2-b]furan-3,6-dicarbaldehyde, D.
  • Example 4 Synthesis of ((3S,3aR,6S,6aR)-hexahydrofuro[3,2-b]furan-3,6- diyl)dimethanamine, E.
  • the flask head space was purged with two balloon volumes of H 2 , followed by one volume that channeled through the needle.
  • the reaction mixture was stirred under the H 2 blanket for 4 hours, then filtered through a CELITETM pad.
  • the flask head space was purged with two balloon volumes of H 2 , followed by one volume that channeled through the needle.
  • the reaction mixture was stirred under the H 2 blanket for 4 hours, then filtered through a CELITETM pad.
  • Example 1 Synthesis of diiminohexane-isosorbide B and diaminohexane C oligomers isosorbide-3,6-dicarbaldehyde A and 1,6-diaminohexane.
  • Example 2 Synthesis of diiminohexane-isomannide B and diaminohexane C oligomers from isomannide-3,6-dicarbaldehyde A and 1,6-diaminohexane.
  • Example 1 Synthesis of (1R,1'R)-1, l'-((3R,3aR,6S,6aR)-hexahydrofuro[3,2-b]furan-3,6- diyl)bis ⁇ ut-3-en -ol) l, (lS,rR) ,r-((3R,3aR,6S,6aR)-hexahydrofuro[3,2-b]furan-3,6-diyl)bis(but- 3-en-l-ol) 2, (lR,rS)-l,r-((3R,3aR,6S,6aR)-hexahydrofuro[3,2-b]furan-3,6-diyl)bis(but-3-en-l-ol) 3, 'S)-l,l'-((3R,3aR,6S,6aR)-hexahydrofuro[3,2-b]furan-3,6-diyl)bis(but-3
  • Example 2 Synthesis of (lR,rR)-l,r-((3S,3aR,6S,6aR)-hexahydrofuro[3,2-b]furan-3,6- diyl)bis(but-3-en-l-ol) 2, and (lS,rR)-l,r-((3S,3aR,6S,6aR)-hexahydrofuro[3,2-b]furan-3,6- diyl)bis(but-3-en-l-ol) 3.
  • Example 3 Synthesis of (lR,l'R)-l,r-((3R,3aR,6R,6aR)-hexahydrofuro[3,2-b]furan-3,6- diyl)bis ⁇ ut-3-en-l-ol) 2, (lS,rR)-l,r-((3R,3aR,6R,6aR)-hexahydrofuro[3,2-b]furan-3,6-diyl)bis(but-
  • Example 1 Synthesis of isomannide-3,6-dimethanamine-terephthalate polyamide B from isomannide-3,6-dimethamine A.
  • Example 2 Synthesis of isosorbide-3,6-dimethanamine-terephthalate polyamide B from isosorbide-3,6-dimethanamine A.
  • Example 3 Synthesis of isoidide-3,6-dimethanamine-terephthalate polyamide B from isoidide-3,6-dimethanamine A.

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  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

L'invention concerne des méthodes de synthèse d'isohexide-3,6-dicarbaldéhydes et/ou d'isohexide-3,6-diméthanamines à partir des produits de déshydratation d'alcools de sucre (isohexides), et dérivés correspondants. Les méthodes consistent tout d'abord à convertir les groupements -OH d'un isohexide en triflates à l'aide l'anhydride triflique à basse température, puis à réaliser une substitution centrée sur le carbone du triflate par un nitrile, pour former des isohexide-3,6-dinitriles cristallins. Les isohexide-3,6-dinitriles sont ensuite soumis à une réaction avec un agent réducteur, tel qu'un hydrure métallique, dans un solvant organique anhydre à très basse température pour générer des isohexide-3,6-dicarbaldéhydes. Dans une étape ultérieure d'amination réductrice, les isohexide-3,6-dicarbaldéhydes sont d'abord convertis en leurs diimines correspondants, lesquels peuvent être isolés, ou ensuite réduit en isohexide-3,6-diméthanamines.
PCT/US2016/065521 2015-12-18 2016-12-08 Préparation d'isohexide-3,6-dicarbaldéhydes et d'isohexide-3,6-diméthanamines Ceased WO2017105985A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117551112A (zh) * 2023-11-24 2024-02-13 吉林大学 一种环状结构为骨架的直链二元醇及其制备方法
KR102638391B1 (ko) * 2023-05-30 2024-02-20 삼화페인트공업주식회사 다이알칸설포닐 아이소소바이드 화합물의 제조 방법, 리튬이차전지용 전해액 첨가제, 리튬이차전지용 전해액 및 리튬이차전지

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US20100222611A1 (en) * 2005-06-30 2010-09-02 Michael Leo Tulchinsky Process for the Reductive Amination of Aldehydes and Ketones Via the Formation of Macrocyclic Polyimine Intermediates
WO2014209595A1 (fr) * 2013-06-28 2014-12-31 Archer Daniels Midland Company Tétrahydrofurane-2,5-dicarbaldéhyde (diformyl-tétrahydrofurane, dfthf) et procédé de synthèse de celui-ci

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* Cited by examiner, † Cited by third party
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US20100222611A1 (en) * 2005-06-30 2010-09-02 Michael Leo Tulchinsky Process for the Reductive Amination of Aldehydes and Ketones Via the Formation of Macrocyclic Polyimine Intermediates
WO2014209595A1 (fr) * 2013-06-28 2014-12-31 Archer Daniels Midland Company Tétrahydrofurane-2,5-dicarbaldéhyde (diformyl-tétrahydrofurane, dfthf) et procédé de synthèse de celui-ci

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102638391B1 (ko) * 2023-05-30 2024-02-20 삼화페인트공업주식회사 다이알칸설포닐 아이소소바이드 화합물의 제조 방법, 리튬이차전지용 전해액 첨가제, 리튬이차전지용 전해액 및 리튬이차전지
CN117551112A (zh) * 2023-11-24 2024-02-13 吉林大学 一种环状结构为骨架的直链二元醇及其制备方法

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