JP6373350B2 - 副生成物の形成を低減させた糖からhmfを作製するプロセス、および安定性が改善されたhmf組成物 - Google Patents
副生成物の形成を低減させた糖からhmfを作製するプロセス、および安定性が改善されたhmf組成物 Download PDFInfo
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- JP6373350B2 JP6373350B2 JP2016500372A JP2016500372A JP6373350B2 JP 6373350 B2 JP6373350 B2 JP 6373350B2 JP 2016500372 A JP2016500372 A JP 2016500372A JP 2016500372 A JP2016500372 A JP 2016500372A JP 6373350 B2 JP6373350 B2 JP 6373350B2
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- Prior art keywords
- hmf
- sugar
- acid
- hexose
- fructose
- Prior art date
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- 229940029339 inulin Drugs 0.000 description 1
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- BAZQYVYVKYOAGO-UHFFFAOYSA-M loxoprofen sodium hydrate Chemical group O.O.[Na+].C1=CC(C(C([O-])=O)C)=CC=C1CC1C(=O)CCC1 BAZQYVYVKYOAGO-UHFFFAOYSA-M 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
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- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
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Images
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/70—Carbohydrates; Sugars; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
- A61K31/34—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having five-membered rings with one oxygen as the only ring hetero atom, e.g. isosorbide
- A61K31/341—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having five-membered rings with one oxygen as the only ring hetero atom, e.g. isosorbide not condensed with another ring, e.g. ranitidine, furosemide, bufetolol, muscarine
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
- A61K47/08—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
- A61K47/10—Alcohols; Phenols; Salts thereof, e.g. glycerol; Polyethylene glycols [PEG]; Poloxamers; PEG/POE alkyl ethers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/08—Solutions
-
- 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
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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
- C07D307/38—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
- C07D307/48—Furfural
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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
- C07D307/38—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
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/06—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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- Furan Compounds (AREA)
- Cosmetics (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
[0048] 結晶性フルクトース(5g)を水7mL中に溶解させ、2つ口25mL丸底フラスコに投入した。フラスコに、溶液中にガス(乾燥空気(比較例1)または窒素(実施例1)のいずれか)をスパージするための管と、還流冷却器とを取り付けた。ガス(乾燥空気または窒素)を溶液中に5分間スパージし、次いで、1滴の濃硫酸を溶液に添加した。次いで、フラスコをゴム製セプタムで密閉し、16ゲージ針を挿入してスパージガスを排出し、7時間還流させた。7時間の反応時間後、乾燥空気でスパージしたものと窒素でスパージしたものの両方による内容物は琥珀色であったが、プロトンNMRにより、窒素でスパージしたものの反応器内容物はレブリン酸およびギ酸を実質的に含んでおらず(表1)、一方、通常の乾燥空気でスパージした反応器内容物は、どちらも顕著な量を示した。
[0050] 溶解したヒドロキシメチルフルフラール500mgの入ったバイアルにブチル化ヒドロキシアニソール(BHA)(実施例2)1000重量ppmを投入した。混合物をボルテックス撹拌し、次いで、85℃に設定したオーブン中に置いた。比較のため、溶解したヒドロキシメチルフルフラール500mgが入っているがBHAが入っていないバイアル(比較例2)を、オーブン中の第1のバイアルの近くに置いた。
[0055] 酸化防止剤BHAが、HMFに加えてHMFのエステルおよびエーテル誘導体も効果的に安定化するかどうかを評価するために、これらの実施例を実施した。
[0059] カラム:Waters BEH C18 2.1×50mm、1.7□m
[0060] 温度:50℃
[0061] 流量:0.5mL/分
[0062] パージ溶媒:10%アセトニトリル
[0063] 洗浄溶媒:50%アセトニトリル
[0064] 溶媒C:50%アセトニトリル
[0065] 溶媒D:水
[0066] グラジエント:
[0073] 測器:7693オートサンプラーを備えたAgilent 7890 GC
[0074] カラム:DB−5 UI 60m×250□m×0.25□m
[0075] キャリアガス:H2
[0076] 流量:1mL/分(一定)
[0077] 注入温度:200℃
[0078] スプリット:50:1
[0079] 検出器:340℃
[0080] 温度プログラム:初期:50℃
[0081] 勾配1:5°/分で180℃まで
[0082] 勾配2:20℃/分で200℃まで、1分保持
Claims (2)
- 低減酸素環境下で酸への曝露によって水性ヘキソース溶液を脱水することを含み、前記低減酸素環境は前記水性ヘキソース溶液中に不活性ガスをスパージすることにより形成される、1種または複数のヘキソースを含む水溶液からヒドロキシメチルフルフラールを作製するプロセス。
- 前記不活性ガスは窒素または二酸化炭素を含む、請求項1に記載のプロセス。
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US201361782539P | 2013-03-14 | 2013-03-14 | |
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PCT/US2014/018186 WO2014158554A1 (en) | 2013-03-14 | 2014-02-25 | Process for making hmf from sugars with reduced byproduct formation, and improved stability hmf compositions |
Publications (2)
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JP2016517407A JP2016517407A (ja) | 2016-06-16 |
JP6373350B2 true JP6373350B2 (ja) | 2018-08-15 |
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MX (1) | MX354363B (ja) |
RU (1) | RU2659166C2 (ja) |
WO (1) | WO2014158554A1 (ja) |
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EP3401312B1 (de) * | 2017-05-08 | 2019-09-04 | AVALON Industries AG | Verfahren zur stabilisierung von 5 hydroxymethylfurfural (hmf) |
DE102018208507A1 (de) | 2018-05-29 | 2019-12-05 | Südzucker AG | Anolytfraktion-katalysierte HMF-Herstellung |
DE102018208510A1 (de) | 2018-05-29 | 2019-12-05 | Südzucker AG | Salz- und Säuregemisch-katalysierte HMF-Herstellung |
EP3807256A4 (en) * | 2018-06-18 | 2021-08-25 | Archer Daniels Midland Company | COLOR STABILIZATION OF MONOMERS AND OTHER REAGENTS TO FORM POLYMERS OF BIOLOGICAL ORIGIN |
CN116178314A (zh) * | 2021-11-29 | 2023-05-30 | 中国科学院宁波材料技术与工程研究所 | 一种提高5-羟甲基糠醛储运稳定性的方法 |
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US2917520A (en) * | 1957-09-11 | 1959-12-15 | Arthur C Cope | Production and recovery of furans |
DE3362937D1 (en) * | 1982-09-28 | 1986-05-15 | Procter & Gamble | Synthesis of sulphonated organic compounds |
CN1038422A (zh) * | 1988-06-10 | 1990-01-03 | 爱德华·A·德朗 | 使用解离的木质纤维材料进行模塑的方法及其产品 |
JPH0399072A (ja) * | 1989-09-11 | 1991-04-24 | Kao Corp | 5―ヒドロキシメチル―2―フランカルボキシアルデヒドの製法 |
EP1834950A1 (en) * | 2006-03-10 | 2007-09-19 | Avantium International B.V. | Method for the synthesis of 5-alkoxymethylfurfural ethers and their use |
EP1834951A1 (en) * | 2006-03-10 | 2007-09-19 | Avantium International B.V. | Method for the synthesis of organic acid esters of 5-hydroxymethylfurfural and their use |
AT503385B1 (de) * | 2006-03-20 | 2008-05-15 | C Y L Pharmazeutika Gmbh | Mittel zur behandlung von oxidativem stress |
US20100218415A1 (en) * | 2007-09-07 | 2010-09-02 | Furanix Technologies B.V. | Hydroxymethylfurfural ethers from sugars and higher alcohols |
UA97690C2 (uk) * | 2007-09-07 | 2012-03-12 | Фураникс Технолоджиз Б.В. | Спосіб одержання суміші простих 5-гідроксиметилфурфуралевих ефірів та паливо або паливна композиція, що містить їх |
BRPI0819406B1 (pt) * | 2007-12-12 | 2021-07-20 | Archer Daniels Midland Co | Método para oxidar um éster de 2-hidroximetil-5-furaldeído (hmf) em ácido 2,5- furanodicarboxílico (fdca) |
WO2011124639A1 (en) * | 2010-04-07 | 2011-10-13 | Novozymes A/S | A method of producing hydroxymethylfurfural |
CN102453007A (zh) * | 2010-10-22 | 2012-05-16 | 王天任 | 一种制备5-羟甲基糠醛的方法 |
JP5779888B2 (ja) * | 2011-01-19 | 2015-09-16 | 三菱化学株式会社 | 2−フルアルデヒド化合物の製造方法 |
JP2012232961A (ja) * | 2011-05-09 | 2012-11-29 | Osaka Prefecture Univ | 温度応答性複合ポリマー |
FR2975396B1 (fr) * | 2011-05-16 | 2013-12-27 | Centre Nat Rech Scient | Procede de preparation de 5-hydroxymethylfurfural |
CN103183653A (zh) * | 2011-12-29 | 2013-07-03 | 广西科学院 | 一种制备5-羟甲基糠醛的绿色方法 |
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CA2902632A1 (en) | 2014-10-02 |
BR112015022816A2 (pt) | 2017-07-18 |
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US20160009675A1 (en) | 2016-01-14 |
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EP2968255B1 (en) | 2018-12-05 |
MX2015011794A (es) | 2016-01-08 |
CA3080500C (en) | 2020-09-08 |
MX354363B (es) | 2018-02-27 |
CA3079120C (en) | 2020-09-08 |
RU2015139512A (ru) | 2017-04-19 |
CA3079120A1 (en) | 2014-10-02 |
AU2014242130B2 (en) | 2017-07-27 |
US9776980B1 (en) | 2017-10-03 |
CN105007913A (zh) | 2015-10-28 |
US9604951B2 (en) | 2017-03-28 |
US20160332978A1 (en) | 2016-11-17 |
CA2902632C (en) | 2020-06-30 |
WO2014158554A1 (en) | 2014-10-02 |
EP2968255A1 (en) | 2016-01-20 |
WO2014158554A8 (en) | 2015-10-15 |
RU2659166C2 (ru) | 2018-06-28 |
CA3080500A1 (en) | 2014-10-02 |
CN105007913B (zh) | 2017-09-29 |
EP2968255A4 (en) | 2016-07-27 |
JP2016517407A (ja) | 2016-06-16 |
KR20150132299A (ko) | 2015-11-25 |
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