EP1773838A1 - Synthesis of aldonolactones, aldarolactones, and aldarodilactones using gas sparging - Google Patents

Synthesis of aldonolactones, aldarolactones, and aldarodilactones using gas sparging

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Publication number
EP1773838A1
EP1773838A1 EP05769130A EP05769130A EP1773838A1 EP 1773838 A1 EP1773838 A1 EP 1773838A1 EP 05769130 A EP05769130 A EP 05769130A EP 05769130 A EP05769130 A EP 05769130A EP 1773838 A1 EP1773838 A1 EP 1773838A1
Authority
EP
European Patent Office
Prior art keywords
acid
mixture
lactone
aldaric
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05769130A
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German (de)
English (en)
French (fr)
Inventor
H. Keith Chenault
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EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1773838A1 publication Critical patent/EP1773838A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • 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

  • This invention is directed to processes for producing lactones or dilactones from aldonic acids, aldaric acids or aldarolactones, or salts thereof.
  • the processes include dehydratively cyclizing a reaction mixture comprising a 5- to 8-carbon aldonic acid, 5- to 8-carbon aldaric acid or 5- to 8-carbon aldarolactone, or mixture thereof, in a solvent mixture, and removing water by gas sparging.
  • Lactones and dilactones derived ultimately from renewable carbohydrate resources are highly functionalized monomers that are useful as synthetic intermediates, chiral starting materials, enzyme inhibitors, and monomers for polymer synthesis.
  • Aldaric acids and aldonic acids are oxidized derivatives of aldose carbohydrates. When only the aldehyde of an aldose is oxidized, an aldonic acid is formed. If both the aldehyde and terminal alcohol of an aldose are oxidized, an aldaric acid is formed. Lactones and dilactones can be produced from these acids via dehydrative cyclization, typically by heating the parent aldonic or aldaric acid under vacuum (Hirasaka, Y., Umemoto, K. Chem. Pharm. Bull. 1965, 13, 325-329). Recent publications and patents demonstrate that this technology has not changed for many years (U.S. Patent No. 6,049,004). Even with heating under vacuum, conversion to the desired lactone is often incomplete
  • Hashimoto, et al. (Hashimoto, K.; et al., Makromol. Chem., Rapid Commun. 1990, 11, 393-396) disclose the synthesis of D-glucaro-1 ,4:6,3- dilactone by repeated lyophilization of glucaric acid from dioxane.
  • Berends and Konings disclose the use of 1-butanol to effect the synthesis of aldonolactones by azeotropic removal of water (Berends, W.; Konings, J. Rec. Trav. Chim. 1955, 74, 1365-1370), but the method suffers from the formation butyl esters as by-products.
  • the present invention provides processes for preparing lactones or dilactones comprising the dehydrative cyclization of a reaction mixture comprising a 5- to 8-carbon aldonic acid, 5- to 8-carbon aldaric acid or 5- to 8-carbon aldarolactone, or mixture thereof, wherein the reaction mixture comprises a solvent mixture and about 10-90 weight % of solids, wherein the solvent mixture comprises about 5 to about 100 volume % of water, and wherein water is removed by gas sparging.
  • the gas is preferably inert.
  • the processes, which rely on dehydrative cyclization can be carried out in an aqueous medium and removal of water is effected by gas sparging.
  • One aspect of the present invention is a process for preparing a lactone or dilactone comprising: a) providing a reaction mixture comprising: i) a solvent mixture comprising about 95 to about 0 volume
  • the reaction mixture comprises an equilibrium mixture of an aldaric acid and one or more of the corresponding aldarolactone or aldarodilactone, or an equilibrium mixture of an aldonic acid and the corresponding aldonolactone.
  • the aldaric acid is glucaric acid.
  • the aldonic acid is gluconic acid.
  • the aldonic acid, aldaric acid or aldarolactone contains one or more protected hydroxyl groups.
  • the hydroxyl groups can be protected as ethers, acetals, carboxylic esters, or sulfonate esters.
  • the 5- to 8-carbon aldonic acid, 5- to 8- carbon aldaric acid or 5- to 8-carbon aldarolactone is D, L, racemic or a nonracemic mixture in its enantiomeric configuration.
  • the reaction mixture can also comprise an aldaric acid that has a plane of symmetry and thus exists in only a meso configuration.
  • the aldonic acid, aldaric acid or aldarolactone is generated in situ from the corresponding Group I, Group II, or ammonium salt, or mixture thereof by acidification.
  • the salt can be a sodium, potassium, lithium, cesium, magnesium, calcium, or ammonium salt
  • the acid can be sulfuric acid, HCI, phosphoric acid, HF, oxalic acid, trifluoroacetic acid, or an acidic cation exchange resin.
  • any precipitate formed during the generation of the aldonic acid, aldaric acid or aldarolactone in situ can be removed.
  • the present invention provides processes for the preparation of a lactone or dilactone by dehydrative cyclization of a 5- to 8-carbon aldonic acid, 5- to 8-carbon aldaric acid or 5- to 8-carbon aldarolactone, or mixture thereof, in a reaction mixture, wherein the reaction mixture comprises a solvent mixture and about 10-90 weight % of solids, wherein the solvent mixture comprises about 5 to about 100 volume % water, and wherein water is removed by gas sparging.
  • the solvent mixture can comprise about 10 to about 90 % of water and at least one non-aqueous solvent.
  • the non-aqueous solvent can be removed by reduced pressure from the solvent mixture.
  • the solvent mixture can comprise, for example, at least one of acetone, methyl ethyl ketone, methanol, ethanol, isopropanol and tetrahydrofuran.
  • the solvent mixture comprises acetone and about 10 to about 50 volume % of water, based on the total volume of the solvent mixture.
  • the reaction mixture can comprise, for example, gluconic, mannonic, galactonic, idonic, allonic, altronic, gulonic, talonic, ribonic, xylonic, arabinonic, lyxonic, glucaric, mannaric, galactaric, idaric, allaric, altraric, ribaric, xylaric or arabinaric acid.
  • an aldaric acid is a derivative of an aldose carbohydrate in which the terminal aldehyde and alcohol groups have been converted to carboxylic acids.
  • An example of an aldaric acid is the aldaric acid derived from glucose, glucaric acid: HOOC-(CHOH) 4 -COOH. Any aldaric acid that can form a lactone or dilactone is suitable for the instant invention, as described below.
  • the aldaric acid can be in any enantiomeric form.
  • Six-carbon aldaric acids that can form two c/s-fused five-membered lactones ( ⁇ -lactones) do so and thus generate dilactone products. The other six-carbon aldaric acids and the five-carbon aldaric acids form monolactones as their ultimate lactonization products.
  • D-glucaric acid has the same 5 absolute structure as L-gularic acid
  • D-altraro-6,3-lactone has the same absolute structure as D-talaro-1 ,4-lactone
  • D-Mannaric acid (CAS Reg. No. 22076-54-60) gives D-mannaro- 1 ,4:6,3-dilactone (CAS Reg. No. 2900-01-8).
  • L-Mannaric acid gives L- mannaro-1 ,4:6,3-dilactone (CAS Reg. No. 214038-58-1 , although this CAS registry number is incorrectly named L-mannonic acid di- ⁇ -lactone).
  • 15 D-ldaric acid (CAS Reg. No. 33012-63-4) gives D-idaro-1 ,4:6,3- dilactone.
  • L-ldaric acid (CAS Reg. No. 80876-58-0) gives L-idaro-1 ,4:6,3- dilactone.
  • L-Altraric acid (CAS Reg. No.
  • Ribaric acid (meso, CAS Reg. No. 33012-62-3) gives (racemic) DL- ribaro-5,2-lactone (CAS Reg. No. 85114-92-7, DL-ribaro-1 ,4-lactone).
  • aldonic acid is a derivative of an aldose carbohydrate in which the terminal aldehyde group has been converted to a carboxylic acid.
  • An example of an aldonic acid is the aldonic acid derived from glucose, gluconic acid: HOOC-(CHOH) 4 -CH 2 OH. Any aldonic acid that can form a lactone is suitable for the instant invention, as described below.
  • the aldonic acid can be in any enantiomeric form.
  • Suitable aldonic acids include, but are not limited to, gluconic, mannonic, galactonic, idonic, allonic, altronic, gulonic, talonic, ribonic, xylonic, arabinonic, and lyxonic acids. Preferred are 5-8 carbon acids; most preferred is gluconic acid.
  • D-Gluconic acid (CAS Reg. No. 526-95-4) gives D-glucono-1 ,4- lactone (1198-69-2).
  • L-Gluconic acid (CAS Reg. No. 157663-13-3) gives L-glucono-1 ,4-lactone (CAS Reg. No. 74464-44-1).
  • D-Mannonic acid (CAS Reg. No. 642-99-9) gives D-mannono-1 ,4- lactone (CAS Reg. No. 26301-79-1).
  • L-Mannonic acid (CAS Reg. No. 51547-37-6) gives L-mannono-1 ,4-lactone (CAS Reg. No. 22430-23-5).
  • D-Allonic acid (CAS Reg. No. 21675-42-3) gives D-allono-1 ,4- lactone (CAS Reg. No. 29474-78-0).
  • L-Allonic acid gives L-allono-1 ,4- lactone (CAS Reg. No. 78184-43-7).
  • D-Altronic acid (CAS Reg. No. 22430-69-9) gives D-altrono-1 ,4- lactone (CAS Reg. No. 83602-36-2).
  • L-Altronic acid gives L-altrono-1 ,4- lactone (CAS Reg. No. 119008-75-2).
  • D-Gulonic acid (CAS Reg. No. 20246-33-7, or CAS Reg. No.
  • D-ldonic acid (CAS Reg. No. 488-33-5) gives D-idono-1 ,4-lactone (CAS Reg. No. 161168-87-2).
  • L-ldonic acid (CAS Reg. No. 1114-17-6) gives L-idono-1 ,4-lactone (CAS Reg. No. 1128-24-1).
  • D-Galactonic acid (CAS Reg. No. 576-36-3) gives D-galactono-1 ,4- lactone (CAS Reg. No. 2782-07-2).
  • L-Galactonic acid (CAS Reg. No. 28278-17-3) gives L-galactono-1 ,4-lactone (CAS Reg. No. 1668-08-2).
  • D-Talonic acid (CAS Reg. No. 20246-35-9) gives D-talono-1 ,4- lactone (CAS Reg. No. 23666-11-7).
  • i_-Talonic acid gives L-talono-1 ,4- lactone (CAS Reg. No. 127997-10-8).
  • D-Ribonic acid (CAS Reg. No. 642-98-8) gives D-ribono-1 ,4-lactone (CAS Reg. No. 5336-08-3).
  • L-Ribonic acid gives L-ribono-1 ,4-lactone (CAS Reg. No. 133908-85-7).
  • D-Arabinonic acid (CAS Reg. No. 488-30-2) gives D-arabinono-1 ,4- lactone (CAS Reg. No. 2782-09-4).
  • L-Arabinonic acid (CAS Reg. No. 608- 53-7) gives L-arabinono-1 ,4-lactone (CAS Reg. No. 51532-86-6).
  • D-Xylonic acid (CAS Reg. No. 526-91-0) gives D-xylono-1 ,4-lactone (CAS Reg. No. 15384-37-9).
  • L-Xylonic acid (CAS Reg. No. 4172-44-5) gives L-xylono-1 ,4-lactone (CAS Reg. No. 68035-75-6).
  • D-Lyxonic acid (CAS Reg. No. 526-92-1) gives D-lyxono-1 ,4-lactone (CAS Reg. No. 15384-34-6).
  • L-Lyxonic acid (CAS Reg. No. 4172-43-4) gives L-lyxono-1 ,4-lactone (CAS Reg. No. 104196-15-8).
  • the starting materials can have one or more hydroxyl groups modified to give either a "deoxy” or a protected derivative.
  • “protected” is meant blocking the reactivity of a hydroxyl group with one or more reagents while a chemical reaction is carried out at an alternative reactive site of the same compound.
  • Protecting groups are well known in the art and any suitable group can be used.
  • Useful hydroxyl protecting groups include ethers, acetals, and carboxylic or sulfonate esters.
  • the starting material may be a mixture of an aldonic or aldaric acid and its various lactone and (if possible) dilactone derivatives. Furthermore, since aldonic and aldaric acids generally exist in both D and L enantiomeric configurations, the starting material may be D, L, racemic (DL), or an unequal mixture of enantiomers. Some aldaric acids have a plane of symmetry and thus exist in only a meso configuration.
  • the starting aldonic or aldaric acid or corresponding lactone may be generated by acidifying a Group I, Group II, or ammonium salt of the parent acid or monolactone.
  • Salts that may serve as precursors include but are not limited to sodium, potassium, lithium, cesium, magnesium, calcium, and ammonium salts.
  • a mixture of salt forms having different cations may also be used as a precursor to the aldonic or aldaric acid.
  • Acids useful for generating aldonic and aldaric acids by acidifying precursor salts include strong mineral acids, carboxylic acids, or polymer bound acids, such as but not limited to sulfuric, hydrochloric, phosphoric, hydrofluoric, oxalic, and trifluoroacetic acids, hydrogen chloride, hydrogen fluoride, and polymeric or solid-phase acids (e.g., strongly acidic cation exchange resins).
  • the starting material may be generated as a solution in water, a suitable organic solvent such as acetone, or a mixture of said solvent and water. Any precipitate formed may optionally be removed by any means, such as filtration, before proceeding.
  • the starting material may optionally be a mixture of different aldonic and/or aldaric acids having different numbers of carbon atoms, different diastereomeric configurations, and/or different numbers of carboxylic acid groups.
  • the mixtures can also be generated in whole or in part by acidifying the appropriate precursor salts.
  • the starting material can be a mixture of one or more of an aldonic acid, an aldaric acid, an aldonolactone, an aldarolactone, and an aldarodilactone.
  • the mixture can be an equilibrium mixture of an aldaric acid or an aldonic acid with its corresponding aldarolactone, aldonolactone, and/or its corresponding aldarodilactone if one exists.
  • the starting materials contain 5-8 carbons.
  • the starting materials are dissolved in a suitable solvent that is comprised of about 5% to about 100 volume % of water to form the reaction mixture.
  • suitable solvent any solvent or mixture of solvents that is substantially inert to all reagents and products, will dissolve the starting materials, and has a boiling point low enough to be removed at a temperature lower than the decomposition temperature of the reactants and products.
  • Suitable solvents include but are not limited to water, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, and isopropanol, and ethers such as THF (tetrahydrofuran).
  • Preferred solvents include water, acetone, and mixtures thereof. Such mixtures can contain from 10 to 90% water by volume, based on the total volume of the solvent mixture, and in some preferred embodiments, from 10 to 50% of water.
  • the solvent can be removed by reduced pressure, such as distillation under reduced pressure. This can be performed at any temperature and pressure that is not detrimental to the reagents or products.
  • the solvent is one that boils at a lower temperature than water, facilitating its removal.
  • water is then added to the starting solution to form a mixture that is substantially free of non-aqueous solvents, which comprises about 10 to 90 weight % solids, preferably 50 to 80 weight % solids, based on the total weight of the mixture.
  • a mixture "substantially free of non ⁇ aqueous solvents", as used herein, means a mixture that contains little or no water, i.e., preferably about 0.5 weight percent or less of any non ⁇ aqueous solvents, or less.
  • a mixture substantially free of non-aqueous solvents may be referred to herein in shorthand manner as an "aqueous mixture".
  • aqueous mixtures that are free of non-aqueous solvents are also intended to be within the scope of the invention.
  • the concentrated aqueous solution is next sparged with a stream of gas.
  • Any gas is suitable provided it does not react with or interact with the reactants, products, or solvent.
  • the gas is dry air, dry nitrogen, dry argon; more preferably dry nitrogen.
  • the gas used for sparging may be pre-heated to make the removal of water more efficient. Additionally, particularly if the volume of the solution is greater than 25 ml_, stirring or other agitation may be used to improve the efficiency of water removal.
  • the sparging removes water, both the water already present as solvent plus the water generated during the lactonization reaction in order to drive lactone (or dilactone) formation to completion.
  • the pressure during the cyclization procedure is preferably from about 1 to about 200 KPa.
  • Stirring or agitation can optionally be used.
  • the temperature of the mixture being dehydrated is kept at about 80 to about 130 0 C.
  • the time required depends on the scale and geometry of the reactor but is typically from about 0.5 to about 5 hours. Completion can be determined by any method, such as periodically removing aliquots and analytically determining % conversion, or by monitoring refractive index or viscosity and color of product melt and absence of condensation.
  • the stirring and sparging are discontinued, and the resulting syrup is allowed to cool to room temperature.
  • the product can be purified using known methods, such as, for example, recrystallization.
  • the solvent-free mixture of the starting materials remains liquid at only moderately high temperatures, for example 80-100 0 C, due to melting point depression.
  • Even essentially pure lactone for example glucaro-1 ,4:6,3-dilactone, remains a syrup during synthesis at temperatures below its melting point (132 0 C) because its crystallization is usually slow kinetically. The sparging removes water in order to maintain this concentration.
  • gluconic acid to gluconolactone a monolactone
  • two lactones are formed: 1 ,4- and 1 ,5- (or ⁇ and ⁇ ). Melting point depression allows them to be formed as a melt at 118-124 0 C when the melting points of the two pure lactones are 133-135 °C and 150-152 0 C, respectively.
  • the stirred mixture was heated at reflux for 4 hours, allowed to cool to room temperature (20-25 0 C), stirred at room temperature for 1-2 hours, and then filtered with suction to remove the precipitated calcium sulfate. At no time did the reaction become homogeneous.
  • the precipitate was washed three times with 150 ml_ of 95:5 acetone-water, each time suspending the precipitate in the solvent and then sucking the solvent through.
  • Acetone was removed from the combined filtrate and washings by distilling under reduced pressure (pot temperature 30 0 C).
  • the concentrated aqueous solution was stirred mechanically with a stream of dry nitrogen passing through and over the surface of the solution.
  • the solution was then heated to 120-130 0 C for 2-3 hours, with continued stirring and nitrogen-sparging, to remove water. Stirring and sparging was then discontinued, and the reaction mixture was allowed to cool to room temperature.
  • the glassy product (85% yield, 92-94% pure) may be further purified by recrystallization. Analysis was performed by 1 H NMR and by GC (silylation with BSTFA- TMSCI, J&W DB-17MS 30 m x 0.32 mm x 0.25 m column, oven temperaturei 20-300 0 C).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Furan Compounds (AREA)
EP05769130A 2004-06-30 2005-06-30 Synthesis of aldonolactones, aldarolactones, and aldarodilactones using gas sparging Withdrawn EP1773838A1 (en)

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US58483504P 2004-06-30 2004-06-30
US58483204P 2004-06-30 2004-06-30
PCT/US2005/023815 WO2006005070A1 (en) 2004-06-30 2005-06-30 Synthesis of aldonolactones, aldarolactones, and aldarodilactones using gas sparging

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EP05787937A Withdrawn EP1773839A1 (en) 2004-06-30 2005-06-30 Synthesis of aldonolactones, aldarolactones, and aldarodilactones using azeotrophic distillation

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WO2006005070A1 (en) * 2004-06-30 2006-01-12 E.I. Dupont De Nemours And Company Synthesis of aldonolactones, aldarolactones, and aldarodilactones using gas sparging
US8669397B2 (en) 2009-06-13 2014-03-11 Rennovia, Inc. Production of adipic acid and derivatives from carbohydrate-containing materials
WO2010144871A2 (en) 2009-06-13 2010-12-16 Rennovia, Inc. Production of glutaric acid and derivatives from carbohydrate-containing materials
US8501989B2 (en) 2009-06-13 2013-08-06 Rennovia, Inc. Production of adipic acid and derivatives from carbohydrate-containing materials
US8669393B2 (en) 2010-03-05 2014-03-11 Rennovia, Inc. Adipic acid compositions
US9770705B2 (en) 2010-06-11 2017-09-26 Rennovia Inc. Oxidation catalysts

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US1830618A (en) * 1930-04-12 1931-11-03 Pfizer Charles & Co Production of lactones
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US4581465A (en) * 1984-03-16 1986-04-08 The Dow Chemical Company Preparation of 1,4-lactones of 3,6-anhydrohexanoic acids
FI92051C (fi) * 1992-03-17 1994-09-26 Amylum Nv Menetelmä ksylitolin valmistamiseksi D-glukoosista ja D-glukoosin ja D-fruktoosin sekä D-glukoosin ja D-galaktoosin seoksista
US5312967A (en) * 1992-08-12 1994-05-17 Uab Research Foundation Process for making activated aldarate esters, ester/lactones and lactones
US6049004A (en) * 1998-12-11 2000-04-11 Kiely; Donald E. Nitric acid removal from oxidation products
EP1283840B1 (en) * 2000-05-26 2005-02-09 E.I. Dupont De Nemours And Company Process for the manufacture of anhydro sugar alcohols
KR100407758B1 (ko) * 2001-08-27 2003-12-01 씨제이 주식회사 스타틴의 제조에 있어서 락톤화 방법
WO2006005070A1 (en) * 2004-06-30 2006-01-12 E.I. Dupont De Nemours And Company Synthesis of aldonolactones, aldarolactones, and aldarodilactones using gas sparging
US20060093702A1 (en) * 2004-07-28 2006-05-04 Andersen Keith C Encapsulation mold assembly and interchangeable cartridge

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JP2008515769A (ja) 2008-05-15
CA2571060A1 (en) 2006-01-12
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JP2008505122A (ja) 2008-02-21
WO2006005071A1 (en) 2006-01-12
CA2571774A1 (en) 2006-01-12

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