- Degradation of 3-Chloro-p-toluidine Hydrochloride in Watermelon Bait. Identification and Chemical Characterization of Novel N-Glucoside and Oxopropanimine
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Stability of the avicide 3-chloro-p-toluidine hydrochloride (CPTH) in watermelon bait was assessed. When exposed to light, the presence of CPTH accelerated nonenzymic browning (Maillard) reactions and degradation of the watermelon matrix. The addition of potassium metabisulfite appeared to hinder bait degradation. These experiments resulted in the identification and chemical characterization of two novel CPTH derivatives: N-β-D-glucopyranosyl-3-chloro-4-methylaniline and N-(3-chloro4-methylphenyl)-2-oxopropanimine.
- Tawara, Jeanne N.,Johnston, John J.,Goodall, Margaret J.
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- Pyrolysis/GC/MS Analysis of 1--1-deoxy-D-fructose (Proline Amadori Compound)
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Pyrolysis/GC/MS was applied to the study of primary and secondary pyrolysis products of 1--1-deoxy-D-fructose (proline Amadori compound). The Amadori product was pyrolyzed on a ribbon probe at 150, 200, 250, 300, and 350 deg C for 10 s. The main products formed under these conditions were 1-(1'-pyrrolidinyl)-2-propanone, 2-hydroxy-1-(1/-pyrrolidinyl)-1-buten-3-one, and 2,3-dihydro-3,5-dihydroxy-6-methyl-4(H)-pyran-4-one in addition to acetic acid and pyrrolidine. The produce secondary pyrolysis products, the Amadori compound was pyrolyzed at 250 deg C in a quartz tube for 20 s; 14 secondary pyrolysis products were identified. The majority of the products were also reported to be formed during autoclaving of proline/monosaccharide mixtures at 150 deg C for 1.5 h in water. In addition, the pyrolysis of D-glucose/proline and the proline Amadori compound was compared. Keywords: Pyrolysis; proline; Amadori compound; decomposition; mechanism; Maillard reaction
- Huyghues-Despointes, Alexis,Yaylayan, Varoujan A.,Keyhani, Anahita
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- Effect of hydroxyl on antioxidant properties of 2,3-dihydro-3,5-dihydroxy-6-methyl-4: H -pyran-4-one to scavenge free radicals
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It is well known that 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one (DDMP) is usually formed in the Maillard reaction and it contributes to the antioxidant properties of Maillard reaction intermediates. A series of hydroxyl group protected DDMP derivatives were synthesized to further understand the source of antioxidant activity. Antioxidant abilities of the DDMP derivatives were evaluated by scavenging the 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonate) cationic radical (ABTS+), 2,2′-diphenyl-1-picrylhydrazyl radical (DPPH), and galvinoxyl radical, respectively. It was found that the introduction of protecting groups to the free hydroxyl groups of DDMP decreases their reducing abilities. In particular, the hydroxyl group at the olefin position exhibited a remarkable impact on the antioxidant activity of DDMP, indicating that the unstable enol structure in the DDMP moiety is the key factor for its antioxidant activity.
- Bai, Bing,Cai, Lili,Chen, Zhifei,Fu, Yufeng,Liu, Qiang,Ma, Yuping,Sun, Zhitao,Wang, Qingfu,Xi, Gaolei,Zhao, Zhiwei
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p. 34456 - 34461
(2021/12/02)
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- Preparation method of 2, 3-dihydro-3, 5-dihydroxy-6-methyl-4H-pyran-4-one
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The invention relates to a preparation method of 2, 3-dihydro-3, 5-dihydroxy-6-methyl-4H-pyran-4-one. Monosaccharide is adopted as the raw material, secondary amine and acid are used as the catalyst,ethanol is taken as the solvent, and Maillard reaction one-pot method is employed to synthesize 2, 3-dihydro-3, 5-dihydroxy-6-methyl-4H-pyran-4-one. At the same time, silica gel chromatographic column-polyamide resin column-silica gel chromatographic column three-time chromatography is adopted for purification to obtain a 2, 3-dihydro-3, 5-dihydroxy-6-methyl-4H-pyran-4-one pure product, and the yield is up to 20.31%, which is far greater than 3.125% reported in literature. The synthesis and purification method has the advantages of simple preparation process, high yield, easy large-scale production and the like, and has wide application prospects.
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Paragraph 0036-0038; 0045-0049
(2020/03/02)
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- Synthesis method of 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one
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The invention relates to a synthesis method of 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one, which creatively uses maltose as an initial raw material to synthesize the 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one. The synthesis method comprises: firstly, generating maltol acetate through acetylation; secondly, carrying out catalytic hydrogenation to obtain dihydromaltol acetate; adding asilylation reagent again to synthesize a dihydromaltol acetate silyl enol ether compound; increasing reaction activity of 5-position methylene and introducing hydroxy to the 5-position through peroxidation to obtain 5-hydroxy-dihydromaltol acetate; and performing a deacetylation reaction to obtain the 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one that is a target compound. According to the technical scheme, the five-step reaction process is simple, the yield is higher than 80%, the purity of the final product reaches 98% or above, large-scale production can be conducted, and the method has a wide application prospect.
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- Formation of Reactive Intermediates, Color, and Antioxidant Activity in the Maillard Reaction of Maltose in Comparison to d -Glucose
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In this study, the Maillard reaction of maltose and d-glucose in the presence of l-alanine was investigated in aqueous solution at 130 °C and pH 5. The reactivity of both carbohydrates was compared in regards of their degradation, browning, and antioxidant activity. In order to identify relevant differences in the reaction pathways, the concentrations of selected intermediates such as 1,2-dicarbonyl compounds, furans, furanones, and pyranones were determined. It was found, that the degradation of maltose predominantly yields 1,2-dicarbonyls that still carry a glucosyl moiety and thus subsequent reactions to HMF, furfural, and 2-acetylfuran are favored due to the elimination of d-glucose, which is an excellent leaving group in aqueous solution. Consequently, higher amounts of these heterocycles are formed from maltose. 3-deoxyglucosone and 3-deoxygalactosone represent the only relevant C6-1,2-dicarbonyls in maltose incubations and are produced in nearly equimolar amounts during the first 60 min of heating as byproducts of the HMF formation.
- Kanzler, Clemens,Schestkowa, Helena,Haase, Paul T.,Kroh, Lothar W.
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p. 8957 - 8965
(2017/10/17)
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- Antioxidant Properties of Heterocyclic Intermediates of the Maillard Reaction and Structurally Related Compounds
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It is well established that a wide range of reductones is formed in the course of the Maillard reaction and that these substances contribute to the oxidative stability of food. The aim of this study was to analyze 12 important heterocyclic intermediates with and without reductone structure as well as structurally related substances under equal conditions to compare their antioxidant properties in detail. For this purpose, five methods were selected including photometrical methods such as the trolox equivalent antioxidant capacity assay and an electron paramagnetic resonance spectroscopic method. Reductones with furan-3-one structure and 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one were reducing in all assays, whereas isomaltol and maltol did not react in assays based on the reduction of metal ions because of their complexing abilities. The introduction of protecting groups to the free hydroxyl functions of selected reductones could nearly eliminate their reducing abilities. In addition, the oxidation products of the different reductive heterocycles were compared after treatment with iodine. Mainly short-chained organic acids such as lactic, glycolic, and glyceric acid are formed as result of the degradation, which indicates 1,3-dicarbonyl cleavage reactions of corresponding tricarbonyl compounds as intermediates of the oxidation.
- Kanzler, Clemens,Haase, Paul T.,Schestkowa, Helena,Kroh, Lothar W.
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p. 7829 - 7837
(2016/10/31)
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- PHARMACEUTICAL COMPOSITION, FOOD OR BEVERAGE CAPABLE OF ENHANCING SYMPATHETIC NERVE ACTIVITY
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It is intended to provide a safe composition for preventing or treating obesity or related complications which has an autonomic nervous control effect, in particular, an effect of enhancing sympathetic nervous activity and an effect of promoting energy metabolism. Thus, a medicinal composition, a food or a drink containing 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one and having an autonomic nervous control effect and an effect of promoting energy metabolism is provided.
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Page/Page column 11-12
(2010/01/29)
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- Oxygen-dependent fragmentation reactions during the degradation of 1-deoxy-d-erythro-hexo-2,3-diulose
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With this work, we report on further insights into the chemistry of 1-deoxy-d-erythro-hexo-2,3-diulose (1-deoxyglucosone, 1-DG). This α-dicarbonyl plays an important role as a highly reactive intermediate in the Maillard chemistry of hexoses. Degradation of 1-DG in the presence of the amino acid l-alanine led to the formation of several products. Lactic acid and glyceric acid were found to be major degradation products. Their formation was dependent on the presence of oxygen. Therefore, a mechanism is postulated based on oxidation leading to a tricarbonyl intermediate. Carbonyl cleavage of this structure should then give rise to carboxylic acids. This mechanism was supported by the isotope distribution observed during degradation of different 13C-labeled d-glucose isotopomers. Furthermore, we identified 3,5-dihydroxy-6-methyl-2,3-dihydro-4H-pyran-4-one (γ-pyranone) to be capable of rehydration forming 1-DG to a minor extent and therefore leading to the same degradation products. The formation of carboxylic acids from γ-pyranone was also dependent on the presence of oxygen in agreement with the postulated oxidative fragmentation. Finally, we investigated the formation of aldehydes expected as retro-aldol products formed within the degradation of 1-DG. Results seemed to rule out this reaction as an important degradation pathway under the conditions investigated herein.
- Voigt, Michael,Smuda, Mareen,Pfahler, Christoph,Glomb, Marcus A.
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experimental part
p. 5685 - 5691
(2011/08/05)
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- Reactivity of 1-deoxy-D-erythro-hexo-2,3-diulose; A key intermediate in the maillard chemistry of hexoses
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Degradation of 1-deoxyhexo-2,3-diulose, a key intermediate in Maillard chemistry, in the presence of L-alanine under moderate conditions (37 and 50 °C) was investigated. Different analytical strategies were accomplished to cover the broad range of product
- Voigt, Michael,Glomb, Marcus A.
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experimental part
p. 4765 - 4770
(2010/06/14)
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- Identifying new volatile compounds in toasted oak
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Toasting wood to be used in barrels for aging wine produces a great number of volatile and odiferous compounds. Three new volatile odorous compounds in toasted oak were identified. Analysis by high-performance gas chromatography of toasted oak extracts, combined with olfactory detection, enabled various chromatographic peaks with these specific aromas to be isolated. These same odors were simultaneously studied by heating glucose both with and without proline and phenylalanine. Aromatic compounds of interest were identified thanks to a combination of gas chromatography and both mass and infrared spectrometry. An analysis RMN was also used. Hydroxymaltol, 2,5-furanedicarbaldehyde, and furylhydroxymethyl ketone have been detected in extract of toasted oak wood. These molecules may be formed by direct pyrolysis of sugar or Maillard reactions. The acetylformoine was not detected in extract of toasted oak wood, whereas it was detected in heated extracts of various sugars and sugars mixtures with amino acids.
- Cutzach, Isabelle,Chatonnet, Pascal,Henry, Robert,Dubourdieu, Denis
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p. 1663 - 1667
(2007/10/03)
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- Analysis of furanone, pyranone, and new heterocyclic colored compounds from sugar-glycine model maillard systems
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Aqueous sugar (xylose or glucose)-glycine model systems were refluxed for 2 h with the pH maintained at 5. Reverse-phase HPLC of the total reaction products gave two resolved peaks (one of which was colored) for the xylose system and five resolved peaks (two of which were colored) for the glucose system. The components responsible for these peaks were isolated from the ethyl acetate extracts by semipreparative HPLC. Using mainly NMR, the colored compound from the xylose system was identified as the new 2-acetyl-6- (hydroxymethyl)-5,6-dihydro-4H-pyridinone. The colored compounds from the glucose system were most likely to be two novel cis/trans ring isomers of the related new compound 2-acetyl-6-hydroxy-7-(hydroxymethyl)-1,5,6,7-tetrahydro- 4H-azepinone. These compounds are the first one-ring structures isolated from sugar-amino acid model systems that are reported to be colored. Two of the colorless components of the glucose system were identified, mainly by NMR experiments, as the related compounds 4-hydroxy-2-(hydroxymethyl)-5-methyl- 3(2H)-furanone and 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyranone. The remaining compound from the glucose system and the colorless compound from the xylose system were identified as 5-(hydroxymethyl)furfural and 4-hydroxy- 5-methyl-3(2H)-furanone, respectively.
- Ames, Jennifer M.,Bailey, Richard G.,Mann, John
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p. 438 - 443
(2007/10/03)
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- Formation of Hydroxyfuranone and Hydroxypyranone Derivatives with DNA-Breaking Activity in the Maillard Reaction of Glucose and Albumin under Physiological Conditions
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Formation of DNA breaking hydroxyfuranone and hydroxypyranone derivatives in the Maillard reaction of glucose and bovine serum albumin (BSA) under physiological conditions was investigated. A mixture of glucose and BSA was incubated at 37 deg C in water or in 1 M phosphate buffer (pH 7.4). The ethyl acetate/2-propanol extract of the reaction mixtures showed significant DNA breaking activity against supercoiled DNA especially in the presence of Fe(III) ion. Gas chromatography/mass spectrometry analysis of the mixture revelaed the formation of DNA breaking hydroxyfuranones (HMF and DMHF) and hydroxypyranone (DDMP).
- Hiramoto, Kazuyuki,Ishihara, Akira,Sakui, Norihiro,Daishima, Shigeki,Kikugawa, Kiyomi
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p. 101 - 104
(2007/10/03)
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- DNA strand-breaking activity and mutagenicity of 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one (DDMP), a Maillard reaction product of glucose and glycine
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Aqueous solution of glucose and glycine was heated under reflux for 4 h and extracted with ethyl acetate. Reversed phase HPLC of the extract revealed a new DNA strand-breaking substance, which was purified by repeated HPLC and identified as 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one (DDMP). DDMP induced DNA strand breaking in a dose- and time-dependent manner. It was active to break DNA strands at pH 7.4 and 9.4. Its pyranone skeleton was destroyed at the pH values. DNA strand breaking by DDMP was inhibited by superoxide dismutase, catalase, scavengers for hydroxyl radical, spin trapping agents and metal chelators, and the breaking was enhanced by Fe(III) ion. A mixture of DDMP and a spin trap DMPO gave electron spin resonance signals of a spin adduct DMPO-OH, indicating generation of hydroxyl radical. DDMP was found to be mutagenic to Salmonella typhimurium TA100 without metabolic activation. These results show DDMP generated active oxygen species to cause DNA strand breaking and mutagenesis.
- Hiramoto, Kazuyuki,Nasuhara, Akiko,Michikoshi, Kae,Kato, Tetsuta,Kikugawa, Kiyomi
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- Retro-aldol and redox reactions of Amadori compounds: Mechanistic studies with variously labeled D-[13C]glucose
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Oxidation-reduction reactions necessary to justify many of the products observed in Maillard model systems are usually attributed to molecular oxygen and the so-called reductons. The proline specific 1-(1′-pyrrolidinyl)-2-propanone and 1-(1′-pyrrolidinyl)-2-butanone are such compounds that require reduction steps to justify their formation. Experimental evidence using glucose separately labeled at 13C1, 13C2, 13C3, 13C4, 13C5, and 13C6 indicates that 1-(1′-pyrrolidinyl)-2-propanone is formed by two related pathways, initiated by a retro-aldol cleavage of proline Amadori compound at C3-C4, and 1-(1′-pyrrolidinyl)-2-butanone is formed by three pathways, one initiated by a retro-aldol reaction at C2-C3 of the 1-(prolino)-1-deoxy-4-hexosulose (an isomer of Amadori product formed by carbonyl migration) and two others by similar retro-aldol reactions at C4-C5 from both 3-deoxyglucosone and 1-(prolino)-1,4-dideoxy-2,3-hexodiulose. All of the proposed mechanisms require reduction steps for the formation of the target compounds. Model studies have indicated that reductions in Maillard systems can be effected by three pathways: through hydride transfer from formic acid; through cyclic dimerization of α-hydroxy carbonyl compounds followed by electrocyclic ring opening to produce oxidation/reduction products; and by disproportionation of enediols with α-dicarbonyl compounds through double proton transfer.
- Huyghues-Despointes, Alexis,Yaylayan, Varoujan A.
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p. 672 - 681
(2007/10/03)
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- On the Role of 2,3-Dihydro-3,5-dihydroxy-6-methyl-4(H)-pyran-4-one in the Maillard Reaction
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To investigate the thermal degradation pathways of 2,3-dihydro-3,5-dihydroxy-6-methyl-4(H)-pyran-4-one (1) in the Maillard reaction, the 13C-labeled and unlabeled 1 were synthesized and heated in model systems of food processing. The extent and position of the labeling of the reaction products were interpreted by the mass spectroscopy data. The volatiles identified were, among others, 2,4-dihydroxy-2,5-dimethyl-3(2H)-furanone (2), 2,5-dimethyl-4-hydroxy-3(2H)-furanone, cyclotene, maltol, 5-hydroxymaltol, and some acyclic carbonyls. Under roasting conditions, 2 was formed as a major product. It was concluded that 1 might be transferred to highly reactive open-chain intermediates like the enolic forms of 1-deoxyosone. The further reaction pathways varied with the reaction conditions. Possible degradation pathways of 1 that resulted from the labeling experiments as well as the formation of the described products are discussed.
- Kim, Myong-Ock,Baltes, Werner
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p. 282 - 289
(2007/10/03)
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- Detection of D-glucose-derived pyrrole compounds during Maillard reaction under physiological conditions.
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5-Hydroxyl-1-neopentylpyrrole-2-carbaldehyde, 2-(2-hydroxyacetyl)-1-neopentylpyrrole, in decreasing order or abundance, have been isolated and the structures characterized. These compounds were obtained from the reaction of a mixture of D-glucose and neopentylamine under physiological conditions of pH and temperature. In addition, 4H-dihydropyran-4-one, a known intermediate product of the Maillard reaction, was detected. The neopentylamine adducts were already detectable after one week of incubation, but rapid acid and alkaline degradation explains the lack of detection in body proteins.
- Njoroge,Sayre,Monnier
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p. 211 - 220
(2007/10/02)
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- Maillard Reaction Products Formed from D-Glucose and Glycine and the Formation Mechanisms of Amides as Major Components
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Equimolar aqueous solution of D-glucose and glycine were heated at 50 oC and 95 oC at pH 6.7.The headspace volatiles and the ether extracts from the reaction mixture were analyzed by gaz chromatography and gas chromatography-mass spectrometry, using a fused silica capillary column.The major components formed were identified as diacetyl, furfuryl alcohol, two pyrroles, one pyranone and two amides.In order to elucidate the formation mechanisms of the amides formed from amino-carbonyl reactions, two model systems were adopted.N-Butylacetamide and N-butylformamide were formed as major components from diacetyl-butylamine and glyoxal- butylamine systems, respectively.The results obtained suggest that such α-dicarbonyls as 3-deoxyosone, 1-deoxy-D-erythro-2,3-hexodiulose and diacetyl generated in the amino-carbonyl reaction react with amino compounds, amides then formed by cleavage of the C-C bond in the α-dicarbonyls.
- Hayase, Fumikata,Kim, Bong Seon,Kato, Hiromichi
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p. 2337 - 2342
(2007/10/02)
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- SYNTHESIS OF A DERIVATIVE OF 1-DEOXY-D-erythro-2,3-HEXODIULOSE AND ITS CONVERSION INTO NONENZYMIC BROWNING PRODUCTS
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A new synthesis of 1-deoxy-4,5-O-isopropylidene-D-erythro-2,3-hexodiulose (5), a stable derivative of the elusive 1-deoxy-D-erythro-2,3-hexodiulose (6), starting from 3,6-anhydro-4,5-O-isopropylidene-D-mannitol (1) is described.Acid hydrolysis of 5 produced 6, which without isolation was treated with piperidine acetate to yield piperidino-hexose-reductone (7) and 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one (8).A third component in the reaction mixture has been tentatively assigned from mass-spectroscopic data the structure 4-hydroxy-2-hydroxymethyl-5-methyl-3(2H)-furanone (9).
- Fisher, Benjamin E.,Sinclair, Henry B.,Goodwin, James C.
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p. 209 - 216
(2007/10/02)
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