WO2016191682A1 - Préparation de chlorures d'acide à partir de 5-(chlorométhyl)furfural - Google Patents

Préparation de chlorures d'acide à partir de 5-(chlorométhyl)furfural Download PDF

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Publication number
WO2016191682A1
WO2016191682A1 PCT/US2016/034653 US2016034653W WO2016191682A1 WO 2016191682 A1 WO2016191682 A1 WO 2016191682A1 US 2016034653 W US2016034653 W US 2016034653W WO 2016191682 A1 WO2016191682 A1 WO 2016191682A1
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Prior art keywords
compound
reaction mixture
formula
furan
chloromethyl
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PCT/US2016/034653
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English (en)
Inventor
Mark Mascal
Saikat DUTTA
Linglin WU
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The Regents Of The University Of California
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Publication of WO2016191682A1 publication Critical patent/WO2016191682A1/fr

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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
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • 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
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom

Definitions

  • CMF 5-(Chloromethyl)furfural
  • CMFCC 5-(chloromethyl)furan-2-carbonyl chloride
  • DFF 2,5-diformylfuran
  • FDCC diacid chloride furan-2,5-dicarbonyl chloride
  • the synthetically versatile acid chlorides CMFCC 4 and FDCC 11 are two and three simple, efficient steps removed from raw biomass, respectively, being derived from the HMF- equivalent platform chemical CMF 3.
  • furan-2-carboxylates and furan-2,5- dicarboxylates have been produced from HMF, the process is burdened by the poor accessibility of HMF from biomass.
  • the opportunity to access these acids, which are platform chemicals in their own right, in the form of soluble, conveniently derivatizable acid chlorides, will serve to broaden the scope of commercially relevant biorefinery products that can be derived from carbohydrates.
  • the present invention provides a method of preparing a compound of Formula I: (I)
  • the method comprising forming a reaction mixture of tert-butyl hypochlorite and a compound of Formula II: (II) under conditions sufficient to form the compound of Formula I, wherein R is selected from the group consisting of–CH 2 Cl and–C(O)H.
  • the present invention provides a method of preparing a compound of Formula II having the structure:
  • reaction mixture comprising Bi(NO 3 ) 3 ⁇ 5H 2 O and a compound having the structure:
  • the present invention provides a method of preparing a compound of having the structure:
  • reaction mixture comprising ethanol and a compound having the structure:
  • reaction mixture is heated at a temperature of at least about 100 °C in a closed vessel, thereby forming the compound.
  • the present invention provides a compound selected from the group consisting of:
  • Figure 1 shows [M1]the structures of furan-2,5-dicarboxylic acid (FDCA) 1, 5- (hydroxymethyl)furfural (HMF) (2), and 5-(chloromethyl)furfural (CMF) (3).
  • Figure 2 shows preparation of compound 5 from compound 3 where the reagents and conditions include a) t-BuOCl, 24 h; b) EtOH, 50 °C, 6 h, 82% over 2 steps.
  • Figure 3 shows preparation of compounds 6, 7, 8 and 9 from compound 5 where the reagents and conditions include a) EtOH, 150 °C, 7 h, 96%; b) H 2 , Pd/C, 2.5 h, 86%; c) BnNH 2 , 50 °C, 24 h, 82%; d) 1,3,5-Me 3 Ph, AlCl 3 , 24 h, 95%.
  • Figure 4 shows preparation of compounds 11, 12 and 13 from compound 3 where the reagents and conditions: a) DMSO, 150 °C, 18 h, 81%; b) t-BuOCl, 24 h; c) EtOH, 50 °C, 6 h; 76% over 2 steps; d) PhH, AlCl 3 , 20 h, 66% over 2 steps.
  • Figure 5 shows preparation of compound 10 from compound 3 using Bi(NO 3 ) 3 ⁇ 5H 2 O catalyst.
  • the present invention is drawn to a method of preparing furan acid chlorides from furfurals using tert-butyl hypochlorite.
  • the present invention also includes a method for preparing 2,5-diformylfuran from 5-(chloromethyl)furfural using Bi(NO 3 ) 3 ⁇ 5H 2 O.
  • Several ethyl furan-2-carboxylates are also provided.
  • “Forming a reaction mixture” refers to the process of bringing into contact at least two distinct species such that they mix together and can react, either modifying one of the initial reactants or forming a third, distinct, species, a product. It should be appreciated, however, the resulting reaction product can be produced directly from a reaction between the added reagents or from an intermediate from one or more of the added reagents which can be produced in the reaction mixture.
  • “Bismuth catalyst” refers to a bismuth containing compound capable of increasing the rate of a particular chemical reaction. The bismuth catalyst is regenerated following each chemical transformation, so a less than equimolar amount is required in the chemical reaction. The bismuth can have any suitable oxidation state, including I, II, III, IV and V.
  • “A closed vessel” refers to a reaction vessel that is sealed such that the pressure within the closed vessel can be greater than atmospheric pressure.
  • “Without exposure to visible light” refers to the absence of light having wavelength(s) between about 400 nm and about 750 nm. III.
  • the ethyl 5-(ethoxymethyl)furan-2-carboxylate product 6 is a previously unreported molecule among a class of 5-(alkoxymethyl)furan-2- carboxylate esters that are little known in the chemical literature.
  • the high stability of 6 compared to 5-(ethoxymethyl)furfural, itself a proposed biofuel suggests the potential of a similar application for 6 and its congeners.
  • FDCC 11 is freely soluble in common organic solvents, compared to FDCA 1 which is soluble only in polar aprotic solvents such as DMSO.
  • Derivatization by Friedel-Crafts acylation of benzene with 11 provided the bis(aryl) ketone 13.
  • the present invention describes a method of preparing acid chlorides from furfurals using tert-butyl hypochlorite.
  • the present invention provides a method of preparing a compound of Formula I:
  • compound of Formula I has the structure selected from the group consisting of:
  • the method comprises forming the reaction mixture of tert-butyl hypochlorite and the compound of Formula II having the structure:
  • the method comprises forming the reaction mixture of tert-butyl hypochlorite and the compound of Formula II having the structure:
  • the reaction mixtures of the method for preparation of Formula I can be at any suitable temperature.
  • the temperature of the reaction mixture can be of from about 0 oC to about 200 oC, such as at about 0, 5, 10, 15, 20, 22 (room temperature), 25, 30, 35, 40, 45 or about 50 oC.
  • the temperature of the reaction mixture can be from about 0 oC to about 30 oC, or of from about 10 oC to about 30 oC, or of from about 15 oC to about 25 oC.
  • the temperature of the reaction mixture can be about room temperature.
  • the method also includes, prior to the step of forming the reaction mixture, forming a second reaction mixture comprising a bismuth (III) catalyst and the compound of Formula II having the structure:
  • the present invention also provides methods of preparing diformyl compounds.
  • the present invention provides a method of preparing a compound of Formula II having the structure:
  • reaction mixture comprising Bi(NO 3 ) 3 ⁇ 5H 2 O and a compound having the structure:
  • Representative bismuth (III) catalysts useful in the method of the present invention include, but are not limited to, Bi(NO 3 ) 3 , Bi(NO 3 ) 3 ⁇ 5H 2 O, BiCl 3 , BiBr 3 , Bi(OTf) 3 , Bi(OAc) 3 , Bu 3 Bi, Ph 3 Bi, and others.
  • the bismuth (III) catalyst can be Bi(NO 3 ) 3 , Bi(NO 3 ) 3 ⁇ 5H 2 O, BiCl 3 , BiBr 3 , Bi(OTf) 3 , or Bi(OAc) 3 ,.
  • the bismuth (III) catalyst can be Bi(NO 3 ) 3 ⁇ 5H 2 O.
  • the method of forming the compound of formula II can be performed at any suitable temperature.
  • the temperature of the reaction mixture can be of from about 0 oC to about 200 oC, such as at about 0, 5, 10, 15, 20, 22 (room temperature), 25, 30, 35, 40, 45 or about 50 oC.
  • the temperature of the reaction mixture can be from about 20 oC to about 60 oC, or of from about 30 oC to about 60 oC.
  • the temperature of the reaction mixture can be about 45 oC.
  • the reaction mixture is formed without exposure to visible light.
  • the present invention also provides methods of making ethyl ethers from chloromethyl groups.
  • the present invention provides a method of preparing a compound of having the structure:
  • reaction mixture comprising ethanol and a compound having the structure:
  • reaction mixture is heated at a temperature of at least about 100 °C in a closed vessel, thereby forming the compound.
  • the reaction mixture can be at any suitable temperature.
  • the temperature of the reaction mixture can be of from about 0 oC to about 200 oC, such as at about 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or about 200 oC.
  • the temperature of the reaction mixture can be from about 100 oC to about 200 oC, or of from about 125 oC to about 175 oC.
  • the temperature can be at least about 100 oC.
  • the temperature can be about 150 oC.
  • the reaction mixture can be present in a closed vessel, such that when the vessel is heated, the pressure inside the closed vessel increases.
  • the closed vessel can be of any suitable material, including glass, metal or plastic.
  • the reaction mixtures of the present methods can be at any suitable temperature.
  • the temperature of the reaction mixture can be of from about 0 oC to about 200 oC, such as at about 0, 5, 10, 15, 20, 22 (room temperature), 25, 30, 35, 40, 45 or about 50 oC.
  • the temperature of the reaction mixture can be from about 0 oC to about 30 oC, or of from about 10 oC to about 30 oC, or of from about 15 oC to about 25 oC.
  • the temperature of the reaction mixture can be about room temperature.
  • the reaction mixtures of the method can be at any suitable pressure.
  • the reaction mixture can be at atmospheric pressure or above atmospheric pressure. Pressures greater than atmospheric pressure can be achieved by using a pressure vessel and pressurizing with a suitable gas, or using a closed vessel that is then heated.
  • the reaction mixtures can be also be exposed to any suitable environment, such as atmospheric gases, or inert gases such as nitrogen or argon.
  • the reaction mixtures of the method can also be agitated by any suitable means. For example, the reaction mixtures can be stirred, shaken, vortexed, or others.
  • Each reaction mixture of the method can be mixed for any suitable period of time from minutes to hours.
  • the reaction mixture can be mixed for about 5 minutes, or 10, 15, 20, 30, 45 or 60 minutes, or for about 1, 2, 3, 4, 6, 12, 16, 24, 36 or 48 hours.
  • the reaction mixtures of the method can include a variety of other components.
  • the reaction mixtures can include salts, buffers, stabilizers, solvents, etc.
  • Useful salts include, but are not limited to, sodium chloride, potassium chloride, and others.
  • the present invention also provides compounds prepared by the methods of the invention. In some embodiments, the present invention provides a compound selected from the group consisting of:
  • the present invention provides a compound having the structure: .
  • the present invention provides a compound having the structure: .
  • the present invention provides a compound having the structure: .
  • DFF 2,5-Diformylfuran
  • Laugel, et al. ChemCatChem 2014, 6, 1195.
  • Nitromethane and mesitylene were purchased from Sigma-Aldrich and dried over 4 ⁇ molecular sieves.
  • Anhydrous ethanol, anhydrous benzene, and aluminum chloride were purchased from Sigma-Aldrich and used as received. All chromatographic separations were carried out on silica gel (40-63 ⁇ m particle size) purchased from Dynamic Adsorbents.
  • CMFCC 4 5-(Chloromethyl)furan-2-carbonyl chloride (CMFCC) 4 and ethyl 5- (chloromethyl)furan-2-carboxylate 5
  • CMFCC 4 5-(Chloromethyl)furfural 3 (2.226 g, 15.40 mmol) and tert-butyl hypochlorite (10.5 mL, 10.1 g, 92.7 mmol) were introduced into a 50 mL round-bottomed flask wrapped with aluminum foil. The mixture was stirred rapidly at room temperature under air. After 24 h, a measured amount of 1,4-dioxane was added as an internal standard and the yield of CMFCC 4 was determined to be 85%.
  • Ethyl 5-(ethoxymethyl)furan-2-carboxylate 6 [0046] A solution of ethyl 5-(chloromethyl)furan-2-carboxylate 5 (1.486 g, 7.879 mmol) in ethanol (25 mL) was heated in a closed vessel at 150 °C for 7 h. The solvent was evaporated to give ethyl 5-(ethoxymethyl)furan-2-carboxylate 6 as a yellow oil (1.500 g, 96%).
  • Furan-2,5-dicarbonyl chloride (FDCC) 11 and diethyl furan-2,5-dicarboxylate 12 [0051] 2,5-Diformylfuran 10 (1.315 g, 10.60 mmol) and tert-butyl hypochlorite (14.4 mL, 13.8 g, 127 mmol) were introduced into a 50 mL round-bottomed flask wrapped with aluminum foil. The suspension was stirred rapidly at room temperature under air for 24 h, resulting in a clear yellow solution. A measured amount of 1,4-dioxane was added as an internal standard and the yield of FDCC 11 was determined to be 80%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Furan Compounds (AREA)

Abstract

La présente invention concerne des dérivés chlorures d'acide de l'acide 5-(chlorométhyl)furan-2-carboxylique et de l'acide furan-2,5-dicarboxylique (FDCA) qui peuvent être produits avec un rendement élevé par le traitement des précurseurs aldéhydes 5-(chlorométhyl)furfural (CMF) et 2,5-diformylfurane (DFF) avec du tert-butyl hypochlorite, qui est préparé à peu de frais à partir de tert-butanol et d'eau de Javel du commerce. Le chlorure de 5-(chlorométhyl)furan-2-carbonyle (CMFCC) et le chlorure de furan-2,5-dicarbonyle (FDCC) sont très utiles comme intermédiaires pour la production de biocombustibles de type esters furoate et de polymères de FDCA.
PCT/US2016/034653 2015-05-28 2016-05-27 Préparation de chlorures d'acide à partir de 5-(chlorométhyl)furfural WO2016191682A1 (fr)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107011295A (zh) * 2017-02-15 2017-08-04 合肥利夫生物科技有限公司 一种2,5‑呋喃二甲醛的制备方法
CN109574964A (zh) * 2018-12-21 2019-04-05 厦门大学 一种制备糠酸甲酯的方法
CN109574963A (zh) * 2018-12-21 2019-04-05 厦门大学 一种糠酸酯类化合物的合成方法
WO2019072920A1 (fr) 2017-10-12 2019-04-18 Synphabase Ag Procédé de préparation d'acide 2,5-furanedicarboxylique
CN110143940A (zh) * 2019-05-07 2019-08-20 中国科学技术大学 一种由2,5-呋喃二甲醛制备2,5-呋喃二甲酰氯的方法
CN112552269A (zh) * 2020-12-22 2021-03-26 国网安徽省电力有限公司电力科学研究院 一步合成2,5-呋喃二甲酰氯的方法
CN112625014A (zh) * 2020-12-22 2021-04-09 国网安徽省电力有限公司电力科学研究院 一种由5-氯甲基糠醛制备2,5-呋喃二甲酰氯的方法
JP2021512111A (ja) * 2018-01-31 2021-05-13 フラニックス・テクノロジーズ・ベーフェー 固体リグノセルロース材料の変換方法
JP2021512102A (ja) * 2018-01-31 2021-05-13 フラニックス・テクノロジーズ・ベーフェー 固体リグノセルロース材料の変換の方法

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US3075000A (en) * 1961-08-21 1963-01-22 Shell Oil Co Oxidation of aldehydes
US20060004088A1 (en) * 2002-10-22 2006-01-05 Oct Inc. Furan derivatives for preventing and curing osteoporosis and pharmaceutical compositions containing the same
US20130172584A1 (en) * 2011-12-28 2013-07-04 E I Du Pont De Nemours And Company Process for the production of furfural
WO2014132178A2 (fr) * 2013-02-28 2014-09-04 Rhodia Operations Derives du furfural a titre de vehicule

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3075000A (en) * 1961-08-21 1963-01-22 Shell Oil Co Oxidation of aldehydes
US20060004088A1 (en) * 2002-10-22 2006-01-05 Oct Inc. Furan derivatives for preventing and curing osteoporosis and pharmaceutical compositions containing the same
US20130172584A1 (en) * 2011-12-28 2013-07-04 E I Du Pont De Nemours And Company Process for the production of furfural
WO2014132178A2 (fr) * 2013-02-28 2014-09-04 Rhodia Operations Derives du furfural a titre de vehicule

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107011295A (zh) * 2017-02-15 2017-08-04 合肥利夫生物科技有限公司 一种2,5‑呋喃二甲醛的制备方法
WO2019072920A1 (fr) 2017-10-12 2019-04-18 Synphabase Ag Procédé de préparation d'acide 2,5-furanedicarboxylique
DE102017123797A1 (de) 2017-10-12 2019-04-18 Synphabase Ag Furandicarbonsäure
JP2021512102A (ja) * 2018-01-31 2021-05-13 フラニックス・テクノロジーズ・ベーフェー 固体リグノセルロース材料の変換の方法
JP2021512111A (ja) * 2018-01-31 2021-05-13 フラニックス・テクノロジーズ・ベーフェー 固体リグノセルロース材料の変換方法
CN109574963A (zh) * 2018-12-21 2019-04-05 厦门大学 一种糠酸酯类化合物的合成方法
CN109574964A (zh) * 2018-12-21 2019-04-05 厦门大学 一种制备糠酸甲酯的方法
CN109574963B (zh) * 2018-12-21 2021-06-25 厦门大学 一种糠酸酯类化合物的合成方法
CN110143940A (zh) * 2019-05-07 2019-08-20 中国科学技术大学 一种由2,5-呋喃二甲醛制备2,5-呋喃二甲酰氯的方法
CN110143940B (zh) * 2019-05-07 2022-12-30 中国科学技术大学 一种由2,5-呋喃二甲醛制备2,5-呋喃二甲酰氯的方法
CN112552269A (zh) * 2020-12-22 2021-03-26 国网安徽省电力有限公司电力科学研究院 一步合成2,5-呋喃二甲酰氯的方法
CN112625014A (zh) * 2020-12-22 2021-04-09 国网安徽省电力有限公司电力科学研究院 一种由5-氯甲基糠醛制备2,5-呋喃二甲酰氯的方法
CN112625014B (zh) * 2020-12-22 2023-05-23 国网安徽省电力有限公司电力科学研究院 一种由5-氯甲基糠醛制备2,5-呋喃二甲酰氯的方法

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