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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
D-Fructose (D(-)-Fructose) is a naturally occurring monosaccharide found in many plants.
Synonyms: D(-)-Fructose; Fruit sugar; D-arabino-hexulose
4.5
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| CAS No. : | 57-48-7 |
| Formula : | C6H12O6 |
| M.W : | 180.16 |
| SMILES Code : | [H][C@@](O)(CO)[C@@]([H])(O)[C@]([H])(O)C(=O)CO |
| Synonyms : |
D(-)-Fructose; Fruit sugar; D-arabino-hexulose
|
| English Name : | (3S,4R,5R)-1,3,4,5,6-pentahydroxyhexan-2-one |
| MDL No. : | MFCD00148910 |
| GHS Pictogram: | |
| Signal Word: | |
| Hazard Statements: | |
| Precautionary Statements: | |
| Class: | |
| UN#: | |
| Packing Group: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 29.89 %Chromat. | With Aspergillus flavus NFCCI 2364 culture filtrate In aq. buffer at 55℃; for 24 h; Microbiological reaction | General procedure: FOS production was carried out by adding 1ml of enzyme samples collected at various time intervals to 3ml of 50percent (w/v) sucrose dissolved in 0.1M citrate buffer (pH 5.5) for period of 24h at 55°C. The amount of FOS formation in the samples was analyzed by high performance liquid chromatography (HPLC, Waters) with sugar-pak column (6.5×300mm) and refractive index (RI) differential detector (RI 2414). |
| 25.31 %Chromat. | With Aspergillus niger SI 19 culture filtrate In aq. buffer at 55℃; for 24 h; Microbiological reaction | General procedure: FOS production was carried out by adding 1ml of enzyme samples collected at various time intervals to 3ml of 50percent (w/v) sucrose dissolved in 0.1M citrate buffer (pH 5.5) for period of 24h at 55°C. The amount of FOS formation in the samples was analyzed by high performance liquid chromatography (HPLC, Waters) with sugar-pak column (6.5×300mm) and refractive index (RI) differential detector (RI 2414). |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 84.8% | With erbium(III) chloride In lithium hydroxide monohydrate at 240℃; for 0.5h; Inert atmosphere; Autoclave; | Reaction test and product analysis General procedure: All reactions were carried out in a 35 mL stainless steel autoclaveequipped with a mechanical stirrer. In a typical experiment, 0.1 gof substrate material, 0.05 g of catalyst and 30 mL of water wereadded to the reactor, after which the autoclave was purged threetimes with N2 and then pressurized to 2.0 MPa with N2 at roomtemperature. The reaction mixture was heated to 240 C unless otherwisestated and held at that temperature for 30 min with stirringat 600 rpm. After each reaction the reactor was quickly cooled toroom temperature using an ice/water mixture and then depressurized.The post-reaction sample was diluted with mobile phasesolution prior to analysis.Sample analyses were performed on a Shimadzu LC-20AT HPLCsystem equipped with a RID-10A detector and a Bio-Rad AminexHPX-87H ion exclusion column (300×7.8 mm), using 0.005 MH2SO4 as the mobile phase at a flow rate of 0.5 mL min-1. Thecolumn temperature was 50 C and the detector was set to 45 C.The amount of product was determined using calibration curvesgenerated with standard solutions. |
| 77.3% | With barium hydroxide octahydrate In lithium hydroxide monohydrate at 25℃; for 48h; Inert atmosphere; | 20 Get 1.5774gBa (OH)28H2O is dissolved in the 20mL deionized water, and weigh 0.36g fructose mixes with it again.The velocity of flow with 0.6Lmin lets in high-purity N2, Keep 3min, 25 DEG Cs of constant temperature shaking tables are transferred to with it to rapid airtight reactor later, and the rotational speed be 100rmin, reacts 48h. Absorb 5mL reaction liquid after the reaction, use 5mL0.5MH2SO4Dilute 2 times, get rid of Ba simultaneously2+Influence to the chromatographic column.Dilute back liquid and advance liquid chromatography measurement substrate conversion rate and lactic acid productivity.Obtaining the substrate conversion rate and being 98.3 , the lactic acid productivity is 77.3 , and the lactic acid selectivity is 78.5 . |
| 65% | With sodium hydroxide In lithium hydroxide monohydrate at 100℃; for 0.5h; Autoclave; Inert atmosphere; Green chemistry; chemoselective reaction; |
| 65% | With indium(III) chloride tetrahydrate; sodium picolinate In methanol at 180℃; for 5h; Autoclave; | 1-14 Example 1 14.9 mg (0.05 mmol) of indium (III) chloride tetrahydrate as a metal compound and bis (triphenylphosphine) iminium chloride 28 (0.05 mmol) as a salt, 450.4 mg (2.5 mmol) of fructose as a raw material carbohydrate, 20 mL of methanol as a solvent, and a stirring bar were added to a stainless steel pressure reactor (NITTO KOATSU CHEMICAL INDUSTRIES, LTD ) having an internal volume of 50 ml, and the lid was closed. The air in the autoclave was purged with nitrogen gas and pressurized to 0.5 MPa, and then the autoclave was heated to 150 ° C using an electric furnace while stirring the mixture with a magnetic stirrer. After that, stirring was continued for 5 hours while maintaining at 150 ° C, and then the autoclave was allowed to cool down at room temperature. After cooling, the reaction solution was taken out from the autoclave, and the product in the solution was quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis result is shown in Table 1 below. In addition, the respective yields are represented in percentages (%) of the number of moles (mol) of the product with respect to the number of moles of lactic acids (lactic acids / fructose = 5 mmol / 2.5 mmol), which is theoretically produced from the raw material D- fructose. |
| 61% | With lanthanum trifluoromethanesulphonate at 180℃; for 1h; | |
| With barium dihydroxide | ||
| With potassium hydroxide at 25℃; Einfluss der Alkali-Konzentration; | ||
| With potassium hydroxide at 50℃; Einfluss der Alkali-Konzentration; | ||
| With potassium hydroxide at 75℃; Einfluss der Alkali-Konzentration; | ||
| With anhydrous sodium carbonate | ||
| With calcium hydroxide powder at 165 - 235℃; unter Druck; | ||
| With calcium hydroxide powder at 45℃; unter der Einw. des Sonnenlichts; | ||
| bei der Einw.des Yoghurtfermentes in kuenstlicher Naehrloesung; | ||
| With sodium hydroxide | ||
| With barytes | ||
| With sodium hydroxide | ||
| With barium dihydroxide at 45℃; unter der Einw. des Sonnenlichts; | ||
| With calcium carbonate at 165 - 235℃; unter Druck; | ||
| With lithium hydroxide monohydrate at 50℃; for 2h; | B11 Typical experiments were conducted at 50° C. and consisted of placing 10 ml of fructose or glucose aqueous solution (0.18 M) with 1.2 to 10 ml of resin in a sealed vial, stirring for two hours, filtering the resin, washing with tosylic acid to remove products, and then analyzing the wash solution via HPLC. A summary of these experiments, all conducted at 50° C. for two hours, is given in Table 1. | |
| 36 %Chromat. | Stage #1: D-Fructose With aluminum(III) oxide; potassium hydroxide at 180℃; Microwave irradiation; Stage #2: With sulfuric acid In lithium hydroxide monohydrate | |
| With lithium hydroxide monohydrate; molybdenum(VI) oxide at 100℃; Molecular sieve; | ||
| With Aluminum Chloride; stannous chloride In lithium hydroxide monohydrate at 189.84℃; for 2h; Inert atmosphere; Autoclave; | ||
| 17 %Chromat. | With γ-Al2O3 In lithium hydroxide monohydrate at 170℃; for 4h; Autoclave; | |
| 90.2 %Chromat. | With sodium hydroxide In lithium hydroxide monohydrate for 2h; Inert atmosphere; UV-irradiation; Sealed tube; | |
| 76.4 %Chromat. | With potassium hydroxide In lithium hydroxide monohydrate at 70℃; for 0.5h; Irradiation; |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With sodium hydroxide das Lacton entsteht bei Wasserbadtemperatur unter Luftausschluss; inactive form; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 75% | With immobilized D-psicose epimerase from Corynebacterium glutamicum KCCM 11046 In lithium hydroxide monohydrate at 30 - 50℃; Enzymatic reaction; | 1 Crystalline fructose having a purity of 99% (w/w) or more, a mother liquor collected from continuous chromatography at about 30°C, a mother liquor collected from crystallization at about 30°C, and water at about 30°C were mixed in a solution tank to prepare a substrate 50 brix (%) solution for enzyme reaction.[57]As disclosed in Korean Patent Application No. 10-2009-0118465, enzyme reaction was performed by immobilizing D-psicose epimerase separated from Corynebacterium glutamicum KCCM 11046 at sodium alginate as a carrier, followed by filling isomerization equipment (isomerization tower, manufactured by Hanju Machine Industry Inc.) with the immobilized enzyme, applying the prepared substrate solution for enzyme reaction to the isomerization tower, and heating the substrate solution at 5°C to 20°C per hour up to 50°C through a heat exchanger such that SV [Space Velocity: flow rate (L)/hour (Hr)/resin amount (L)] became 0.5. Here, the resulting D-psicose had a purity of about 24% (w/w).[58]The D-psicose solution having a purity of 24% (w/w) was subjected to first cooling at a rate of 5°C to 10°C per hour down to a temperature of 30°C to 40°C through a heat exchanger, and was then passed through a column filled with a strongly acidic cation exchange resin substituted with hydrogen groups (Lewatit S 1668) and a column filled with a weakly basic anion exchange resin substituted with hydroxyl groups (Lewatit S 4528) such that SV [Space Velocity: flow rate (L)/hour (Hr)/resin amount (L)] became 3, thereby removing ion components remaining in the enzyme reaction solution. Removal of the ion components was measured using a conductivity meter. Here, conductivity was adjusted to not more than 10 microsiemens per cm, and the purity of D-psicose was maintained at 24% (w/w).[59]The ion purified D-psicose-containing solution was introduced into a low temperature evaporator (Forced Thin Film Evaporator, Welcronhantec Co., Ltd.), concentrated to 60 brix (%) (D-psicose solution×100/total solution) at 65°C to 75°C for a short period of time from 10 minutes to 15 minutes. The resulting solution was subjected to second cooling at a rate of 5°C to 25°C per hour through a heat exchanger, and was then passed through a column filled with a strongly acidic cation exchange resin with calcium active groups attached thereto at 50°C to 60°C. Through such continuous chromatography, a fraction containing D-psicose having a purity of 95% (w/w) or more and a fraction containing D-fructose having a purity of 75% (w/w) or more were separated.[60]The mother liquor separated through continuous chromatography, namely, the D-fructose fraction having a purity of 75% (w/w) or more, was collected and cooled at a rate of 20°C to 30°C per hour. When the fraction reached 30°C, the fraction was re-circulated to an enzyme reaction process.[61]The D-psicose solution having a purity of 95% (w/w) or more separated through continuous chromatography was concentrated to 80 brix (%) at 65°C to 75°C in a short period of time from 10 minutes to 15 minutes. The concentrated D-psicose solution having a purity of 95% (w/w) or more was rapidly cooled to 40°C at a rate of 5°C to 20°C per hour through a heat exchanger. The heating and cooling were repeated 5 times to 10 times within the temperature range from 35°C to 40°C such that crystallization was performed for 80 hours to 120 hours, thereby obtaining D-psicose (see Fig. 1). In addition, the mother liquor separated through crystallization, namely, a D-psicose fraction having a purity of 90% or more, was collected, cooled to 30°C, and passed through a column filled with a strongly acidic cation exchange resin substituted with hydrogen groups and a column filled with a weakly basic anion exchange resin substituted with hydroxyl groups.[62]Through the above procedures, the D-psicose solution was concentrated for a short period of time in a low temperature evaporator while the process temperature was adjusted to a low temperature through the heat exchanger, thereby obtaining a high purity D-psicose having a purity of 99% or more with outstanding yield of 75% or more. |
| With triethylamine In ethanol for 15h; Heating; Yield given; | ||
| With D-tagatose 3-epimerase at 25℃; Enzymatic reaction; |
| With 3-epimerase from Clostridium cellulolyticum H10 Heating; aq. buffer; Enzymatic reaction; | ||
| With D-tagatose epimerase from the mesophile Pseudomonas cichorii In aq. phosphate buffer at 25℃; Enzymatic reaction; | ||
| Multi-step reaction with 2 steps 1.1: adenosine triphosphate; magnesium ion; manganese cation; Pseudomonas Sp. St-24 D-tagatose 3-epimerase; Thermotoga maritima MSB8 L-rhamnulose kinase / 45 °C / pH Ca. 7.5 / Enzymatic reaction 2.1: silver(I) nitrate / lithium hydroxide monohydrate 2.2: 37 °C / pH 5.5 / Enzymatic reaction | ||
| With psicose 3-epimerase; manganese cation at 60℃; for 2h; Enzymatic reaction; | 6 D-psicose production by Psicose 3-epimerase D-psicose production by Psicose 3-epimerase [00159] The reaction of the psicose 3-epimerase is performed in a 50 mM PIPES buffer solution containing 14 units of psicose 3-epimerase/ml, 1 mM of Mn2+ ions, and 700 g/L D- fructose at pH 7.0 and at temperature to 60° C. at various times to allow the reaction to proceed sufficiently. The reaction is terminated by heating the reaction solution at 100° C. for 5 minutes, and the enzyme activity is measured by analyzing the reaction mixture for the content of D- psicose and D-fructose. D-psicose production in 120 minutes reaction time is determined. In general the rare sugars are not metabolized by the biological systems and therefore to separates the rare sugars from natural sugars, a fermentation based procedure can be followed to purify the rare sugar from natural sugars. For example, in this example, to purify D-psicose from D- fructose, the mixture containing both these sugars can be mixed with certain microbial strains which can ferment D-fructose but no D-psicose. Upon complete consumption of fructose in the mixture by the microbial cells, the microbial cells are removed by centrifugation or filtration methods and the D-psicose is recovered in an aqueous or organic solution. Although this method is explained with the example of D-psicose, the approach can be used in purifying any other non-fermentable sugars including D-tagatose and L-fructose. | |
| With D-tagatose 3-epimerase from Pseudomonas cichorii, expressed with E. coli JM109 In lithium hydroxide monohydrate at 55 - 60℃; Enzymatic reaction; | 1 EXAMPLE 1-FULL PROCESS, MEMBRANE REACTOR Crystalline fructose is employed as starting material for allulose production. The fructose is dissolved in water and the concentration is adjusted to 40 wt.-%, dry matter, relative to the total weight of the composition. The added water may be tap water, demineralized water, condensed water as provided in a subsequent step of the process, or a mixture of any of the foregoing. The pH value and electrolyte content is adjusted by adding appropriate buffers and salts. (0310) The enzymatic conversion is performed in a membrane reactor (cut off 10 kDa) that is coupled to an ultrafiltration device. The enzymes in the reactor are freely dissolved, i.e. neither immobilized nor contained in microorganisms. (0311) Purified lyophilized enzyme (D-tagatose 3-epimerase from Pseudomonas cichorii, expressed with E. coli JM109) or crude extract (cell free fermentation broth) is added to an aqueous solution of fructose at a concentration within the range of from 50 g/L to 500 g/L in 50 mM TRIS/HCl buffer and 1 mM MnCl2. The pH value is adjusted to pH 7.5 or pH 9 by means of the required amount of HCl aq. and the stirred solution is incubated at 55° C. or 60° C. Depending upon the concentration of the fructose, after 1 hour a yield of 30% allulose relative to the employed fructose may be achieved: [table-us-00006-en] g/L reaction time initial 1 h 24 h fructose fructose allulose yield fructose allulose yield [g/L] [g/L] [g/L] [%] [g/L] [g/L] [%] 51 35 16 30 37 16 31 101 70 30 30 70 30 30 229 165 65 28 168 72 31 420 326 95 23 291 124 30 (0312) The composition containing the fructose is filtered through a filter (0.2 micrometer) and supplied to the membrane reactor. Fructose is converted to allulose by enzymatic catalysis for 36 hours at 30° C. The product is removed from the reactor by ultrafiltration thereby separating the carbohydrates (essentially allulose and residual fructose) from the enzymes which in turn are recycled to the membrane reactor for reuse. (0313) The composition is pre-purified. Decoloring is achieved by means of a decoloring column or by means of active charcoal, in either case at a temperature within the range of from 30° C. to 70° C. Desalting is achieved by means of ion exchange resins, commencing with cations exchangers, followed by anions exchangers, followed by mixed bed exchangers. (0314) The thus provided composition is concentrated by means of an evaporator at a temperature of below 60° C. and the concentration of dry matter is adjusted to a concentration within the range of from 40 wt.-% to 70 wt.-%, relative to the total weight of the composition. The evaporator is selected from rising film plate evaporator (or vertical long tube evaporator), falling film evaporator, Robert evaporator and circulation evaporator, wherein in either case single step or multiple step evaporations are possible. Allulose and residual fructose are separated from one another by chromatography. The chromatography is selected from batch chromatography, continuous chromatography, simulated moving bed (SMB) chromatography and sequential simulated moving bed (SMB) chromatography (SSMB). (0315) The thus provided composition is again concentrated by means of an evaporator at a temperature of below 60° C. and the concentration of dry matter is adjusted to a concentration within the range of from 70 wt.-% to 95 wt.-%, relative to the total weight of the composition. The evaporator is selected from rising film plate evaporator (or vertical long tube evaporator), falling film evaporator, Robert evaporator and circulation evaporator, wherein in either case single step or multiple step evaporations are possible. (0316) From the thus provided composition allulose is provided as a solid material by cooling crystallization and subsequent centrifugation, or by evaporation crystallization and subsequent centrifugation, or by high shear blending and subsequent grinding and sieving, or by spray drying, or by spray granulation, or by spray crystallization, or by means or a belt dryer, or by means of an infrared dryer. The allulose is then (further) dried by means of a drum dryer, or by means of a fluidized bed dryer, or by means of a vibration fluidized bed dryer, or by means of a revolver dryer. The solid allulose is them packaged in bags and palletized. | |
| With Microbacterium foliorum SYG27B-MF Microbiological reaction; Enzymatic reaction; |

[ 57-48-7 ]
[ CAS Unavailable ]
[ 79-14-1 ]
[ 50-21-5 ]
[ 1518-62-3 ]
[ 50-99-7 ]
[ CAS Unavailable ]| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 10 % Chromat. | With potassium hydroxide; Na2B2O7 In water at 78℃; for 0.5h; isomerization equilibrium; degradation to acids; varying time, borate molar ratio from 0.4 to 4.0; | |
| With potassium hydroxide In water at 78℃; for 0.333333h; isomerization equilibrium; degradation to acids; varying time, OH(1-) concentration 0.001 M to O.1 M; also in presence of Ca(2+) up to 0.06 M; |
[ 57-48-7 ]
[ CAS Unavailable ]
[ 79-14-1 ]
[ 50-21-5 ]
[ 1518-62-3 ]
[ 498-43-1 ]
[ CAS Unavailable ]| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With potassium hydroxide In water at 78℃; for 7h; other var. monosaccharines, effects of hydroxyl ion and monosaccharide concentration, effects of inorganic cations and anions, effects of temperature; |
[ 50-99-7 ]
[ CAS Unavailable ]
[ 79-14-1 ]
[ 50-21-5 ]
[ 57-48-7 ]
[ 1518-62-3 ]
[ CAS Unavailable ]| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 50 % Chromat. | With potassium hydroxide; Na2B2O7 In water at 78℃; for 0.5h; isomerization equilibrium; degradation to acids; varying time, borate molar ratio from 0.4 to 4.0; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With hydrogen In water at 25℃; for 15h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With Zeolite Na-X; water at 85℃; for 10h; var. reag.: var. minerals and zeolites; var. pH, isomerization; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With hydrogen cation |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With sodium hydroxide In water at 20℃; for 18h; | 13 EXAMPLE 13 This Example details the synthesis of fructose hydroxypropyl trimethylammonium chloride. A round bottom 250 ml flask was fitted with a mechanical stirrer. Into the flask was charged 1 M sodium hydroxide (55.5 ml, 55.5 mmol), Cornsweet (10 g, 55.5 mmol) and 3-chloro-2-hydroxypropyl trimethylammonium chloride (15 ml, 55.5 mmol). Cornsweet is obtained from the Archer Daniels Midland Corporation as a 100% fructose material. The 3-chloro-2-hydroxypropyl trimethyl ammonium chloride was sourced from Aldrich Chemical Company as a 60% active material in water. It is also available as Quat 188 from the Dow Chemical Company. The reactants were stirred at room temperature for 18 hours. Water was removed under reduced pressure at 50° C. to give a heterogeneous colorless syrup. Filtration through glass wool afforded fructose hydroxypropyl trimethylammonium chloride as a homogeneous clear and colorless syrup: m/z (ESI; M+ -Cl-) 296; HPLC (Column: YMC-ODS-AQ, S5, 120A, 4.6*250 mm; Flow: 1 ml/min isocratic,1 00% water; Detector: RI; Temperature: 35° C.) tr 3.16 min (Cornsweet-tr 3.17 min; CHPTMAC-tr 3.39 min). |

[ 67-47-0 ]
[ 57-48-7 ]
[ 59432-60-9 ]
[ 50-99-7 ]
[ 81129-73-9 ]
[ 470-69-9 ]
[ 13133-07-8 ]| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With water;phosphoric acid; at 50 - 95℃; for 0.25 - 0.75h;pH 1.75 - 3.75; | Figure 4, from a second laboratorial work, is a TLC - Thin Layer Chromatography on silicagel 60 (Merck) developed with the mixture isopropanol : ethyl acetate : water 5:1 :2 as mobile phase and with partial runs of 1/3, 2/3, and 3/3 of the front line and developed with orcinol : sulfuric acid : methanol at 1000C for 5 minutes. This figure illustrates the profile of FOS - Fructooligosaccharides when one hydrolyzes purified inulin from dahlia roots (5g%) with phosphoric acid at pH = 2.5 at 850C during 15 minutes (15), 30 minutes (30), and 45 minutes (45), indicating that the modulation of a single kinetic parameter - time of hydrolysis - already allows to govern the quantitative relation of FOS > fructose (cases 15 and 30) or the opposite (FOS < fructose; 45). A similar strategy for FOS > fructose may also be governed by the other parameters (pH itself or temperature of hydrolysis), as shown for hydrolysis of inulin with phosphoric or citric acids at pHs from 1.75 to 3.75 in the range of 5O0C to 95oC (as better explained in Figure 5). In Figure 4, (f) and (g) denotes for free fructose and glucose, respectively. GP refers to the Degree of Polymerization. It is remarkable that phosphoric or citric hydrolyses of inulin may be effectively addressed <n="27"/>to the preferential preparation of FOS - Fructooligosaccharides since when addressed to a higher fructose content (lane 45), some amount of the co-product HMF - hydroxymethylfurfural turns clearly visible in the front zone of the chromatogram. Its companion spot most probably is a DFA (difructose anhydride).; Figure 5 is a bar graphic comparing the effect of the kinetic parameters such as temperature and time of hydrolysis once fixed the hidrogenionic potential at pH = 2.5 and their respective capacities for the modulation on the qualitative nature of the products from the hydrolyses of dahlia inulin with phosphoric or citric acids when the substrate is used at a concentration of 5g%. According to the intended innovation in this patent request - the preferential production of FOS or FrutoOligoSaccharides - is obviously that, for each range of temperature, namely, 750C, 850C ou 950C, either in the phosphoric or in the citric hydrolyses, the formation of FOS is preferential in (8x2 =) 16 assays, except for those two - at 950C and during 25 minutes - where fructose shows predominance with respect to FOS. Incidentally, those two exceptional conditions - which are not the scope of this patent request - also led to the formation of some HMF - hydroxymethylfurfural - undesirable in a inulin hydrolysis, with the attenuating condition that a less expensive practice as activated charcoal is able to remove the contaminant HMF. Concerning the reaction yield reported to the initial inulin input, the diluted phosphoric acid guarantees in the times of 25 min at 850C and of 15 min at 950C percentages of hydrolyses up to 80%, being the most of the products - 76% and 63%, respectively - FOS or frutooligosaccharides and being the remaining fructose since HMF is no longer detected under these conditions of hydrolysis. The same approach is attained with citric acid although with somewhat reduced yields - 64% or 76%, but even so FOS correspond to 78% and 74% of the hydrolysis products.; Figure 6 derives from another practical example of laboratory work, namely a high performance liquid chromatography or HPLC in a column of 10 micra microparticles of silica gel derivatized with amino groups and provided by Spectraphysics. Twenty microliters of a citric hydrolyzate of inulin at 10% obtained at pH 2.5 during 5 or 15 minutes at 850C were applied to the column and elution proceeded with 70% acetonitrile at a 1 mL/min flow rate and the monitoring was carried out with DRI- differential refraction index. It is shown that in both conditions <n="28"/>- 5 and 15 minutes - inulin is converted, by citric acid, into a family of FOS - FructoOligoSaccharides with DP - Degree of Polymerization - 3 to 18 or more (considering the analytical capacity of the referred column), still emphazing that fructose, with respect to FOS concentration, contributes with a maximum of 25% and a minimum of 5%.; Figure 7, resulting from another practical laboratory work, is also - like Figure 6 - a HPLC but carried out with samples arising from phosphoric acid hydrolyses under the same conditions of those described in Figure 6. The qualitative profiles for FOS are quite similar in both figures. In 8 of 9 assays, FOS predominates. In the nineth - 25 minutes of hydrolysis at higher temperature - FOS and fructose contents are more or less equivalent. |

[ 67-47-0 ]
[ 57-48-7 ]
[ 59432-60-9 ]
[ 81129-73-9 ]
[ 470-69-9 ]
[ 13133-07-8 ]| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With water;citric acid; at 50 - 95℃; for 0.25 - 0.75h;pH 1.75 - 3.75; | Figure 4, from a second laboratorial work, is a TLC - Thin Layer Chromatography on silicagel 60 (Merck) developed with the mixture isopropanol : ethyl acetate : water 5:1 :2 as mobile phase and with partial runs of 1/3, 2/3, and 3/3 of the front line and developed with orcinol : sulfuric acid : methanol at 1000C for 5 minutes. This figure illustrates the profile of FOS - Fructooligosaccharides when one hydrolyzes purified inulin from dahlia roots (5g%) with phosphoric acid at pH = 2.5 at 850C during 15 minutes (15), 30 minutes (30), and 45 minutes (45), indicating that the modulation of a single kinetic parameter - time of hydrolysis - already allows to govern the quantitative relation of FOS > fructose (cases 15 and 30) or the opposite (FOS < fructose; 45). A similar strategy for FOS > fructose may also be governed by the other parameters (pH itself or temperature of hydrolysis), as shown for hydrolysis of inulin with phosphoric or citric acids at pHs from 1.75 to 3.75 in the range of 5O0C to 95oC (as better explained in Figure 5). In Figure 4, (f) and (g) denotes for free fructose and glucose, respectively. GP refers to the Degree of Polymerization. It is remarkable that phosphoric or citric hydrolyses of inulin may be effectively addressed <n="27"/>to the preferential preparation of FOS - Fructooligosaccharides since when addressed to a higher fructose content (lane 45), some amount of the co-product HMF - hydroxymethylfurfural turns clearly visible in the front zone of the chromatogram. Its companion spot most probably is a DFA (difructose anhydride).; Figure 5 is a bar graphic comparing the effect of the kinetic parameters such as temperature and time of hydrolysis once fixed the hidrogenionic potential at pH = 2.5 and their respective capacities for the modulation on the qualitative nature of the products from the hydrolyses of dahlia inulin with phosphoric or citric acids when the substrate is used at a concentration of 5g%. According to the intended innovation in this patent request - the preferential production of FOS or FrutoOligoSaccharides - is obviously that, for each range of temperature, namely, 750C, 850C ou 950C, either in the phosphoric or in the citric hydrolyses, the formation of FOS is preferential in (8x2 =) 16 assays, except for those two - at 950C and during 25 minutes - where fructose shows predominance with respect to FOS. Incidentally, those two exceptional conditions - which are not the scope of this patent request - also led to the formation of some HMF - hydroxymethylfurfural - undesirable in a inulin hydrolysis, with the attenuating condition that a less expensive practice as activated charcoal is able to remove the contaminant HMF. Concerning the reaction yield reported to the initial inulin input, the diluted phosphoric acid guarantees in the times of 25 min at 850C and of 15 min at 950C percentages of hydrolyses up to 80%, being the most of the products - 76% and 63%, respectively - FOS or frutooligosaccharides and being the remaining fructose since HMF is no longer detected under these conditions of hydrolysis. The same approach is attained with citric acid although with somewhat reduced yields - 64% or 76%, but even so FOS correspond to 78% and 74% of the hydrolysis products.; Figure 6 derives from another practical example of laboratory work, namely a high performance liquid chromatography or HPLC in a column of 10 micra microparticles of silica gel derivatized with amino groups and provided by Spectraphysics. Twenty microliters of a citric hydrolyzate of inulin at 10% obtained at pH 2.5 during 5 or 15 minutes at 850C were applied to the column and elution proceeded with 70% acetonitrile at a 1 mL/min flow rate and the monitoring was carried out with DRI- differential refraction index. It is shown that in both conditions <n="28"/>- 5 and 15 minutes - inulin is converted, by citric acid, into a family of FOS - FructoOligoSaccharides with DP - Degree of Polymerization - 3 to 18 or more (considering the analytical capacity of the referred column), still emphazing that fructose, with respect to FOS concentration, contributes with a maximum of 25% and a minimum of 5%. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 45% | With acetic acid In water at 80℃; for 18h; | |
| With acetic acid |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| In methanol at 25℃; aq. phosphate buffer; |
[ 57-48-7 ]
[ 67-63-0 ]
[ 67-56-1 ]
[ 57-55-6 ]
[ 623-61-0 ]
[ 107-21-1 ]
[ 116-09-6 ]
[ 67-64-1 ]
[ 56-81-5 ]| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| In water at 300 - 375℃; Autoclave; | 3 Example 3; Various batch reactions using the Materials of Example 2 were completed. Table 2 presents the yields of products according to the methods of the invention generated from several simple sugars. In these runs aqueous solutions of the sugar at room temperature were pumped into the hot alcohol under pressure. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With sulfuric acid; hydrogen In anhydrous ethylene glycol dimethyl ether at 180℃; for 3h; | 4 EXAMPLE 4:; SYNTHESIS OF AMINOMETHYLFURANS FROM FRUCTOSE IN AN INERT SOLVENT; Crystalline fructose (10 g) was placed in a 100 mL reaction vessel with PEGE-500 (50 g), ( a polyethylene glycol dimethyl ether polymer having an average molecular weight of about 500), dimethylformamide (13 g), sulfuric acid (0.20 mL), and G-69B catalyst (0.50 g). The solution was heated to 180°C for 3 hours. The solution was allowed to cool to room temperature and filtered to remove the resin catalyst. GC/MS indicated complete conversion of fructose and formation of 5- [(dimethylamino)methyl]-furfuryl alcohol. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| In aq. phosphate buffer; dimethyl sulfoxide at 30℃; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 8.25%Chromat.; 29.89%Chromat.; 25.26%Chromat. | With Aspergillus flavus NFCCI 2364 culture filtrate; In aq. buffer; at 55℃; for 24h;pH 5.5;Microbiological reaction; | General procedure: FOS production was carried out by adding 1ml of enzyme samples collected at various time intervals to 3ml of 50% (w/v) sucrose dissolved in 0.1M citrate buffer (pH 5.5) for period of 24h at 55C. The amount of FOS formation in the samples was analyzed by high performance liquid chromatography (HPLC, Waters) with sugar-pak column (6.5×300mm) and refractive index (RI) differential detector (RI 2414). |
| 5.94%Chromat.; 23.74%Chromat.; 25.31%Chromat. | With Aspergillus niger SI 19 culture filtrate; In aq. buffer; at 55℃; for 24h;pH 5.5;Microbiological reaction; | General procedure: FOS production was carried out by adding 1ml of enzyme samples collected at various time intervals to 3ml of 50% (w/v) sucrose dissolved in 0.1M citrate buffer (pH 5.5) for period of 24h at 55C. The amount of FOS formation in the samples was analyzed by high performance liquid chromatography (HPLC, Waters) with sugar-pak column (6.5×300mm) and refractive index (RI) differential detector (RI 2414). |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With Viscozyme L (-fructosyltransferase) immobilized on chitosan spheres; In aq. acetate buffer; at 50℃;pH 4.5;Flow reactor; | Production of invert sugar was carried using a solution of sucrose150 g/L diluted in 50 mM sodium acetate buffer pH 4.5. The solu-tion was pumped at flow rates of (0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0,4.7) mL/min in both fluidized and packed bed reactors. Four bed vol-umes of solution were passed through the column before taking the sample to achieve stationary state. These experiments were carriedout in duplicate, changing the column bed at each experiment |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 49% | With FAD; Escherichia coli L-rhamnulose-1-phosphate aldolase; Streptococcus pneumonia glycerol phosphate oxidase; In water-d2; at 30℃; for 22h;pH 7;Enzymatic reaction; | General procedure: To a solution of DL-glycerol 3-phosphate magnesium salt (548.78 mg, 2.4 mmol) in 6.86 mL ddH2O was added <strong>[497-09-6]D-glyceraldehyde</strong> (or L-glyceraldehyde) (2 mL, 0.5 M, 1.0 mmol) at pH 7.0, glycerol phosphate oxidase saturated with FAD (final concentration 0.2 mg/mL), catalase (1000 U, 1.18 muL) and aldolase (final concentration 0.5 mg/mL). ddH2O was added to bring the total volume to 10 mL if necessary. The reaction mixture was shaken at 30 °C for 22 h and the reaction was monitored by TLC (developed by nBuOH/AcOH/H2O 2/1/1 (v/v/v) and stained with anisaldehyde sugar stain). The pH was then adjusted to pH ~5 with 6 N HCl and 11 muL acid phosphatase (18 U) was added and the mixture was shaken at 37 °C for 24 h. After cooling to rt., the pH was adjusted to 7.0 with 1 N NaOH and the mixture was diluted with methanol. The solution was filtered through Celite and washed with methanol. The filtrate was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (EtOAc/iPrOH/H2O 9/3/1 (v/v/v)) to afford a pale yellow syrup which was further purified by Bio gel P-2 column. The mixture of monosaccharides could be isolated by Ca2+ exchange resin column. The purification process using P-2 column or Ca2+ exchange resin column was performed with the same procedure we previously used. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With FAD; Thermus thermophilus HB8 L-fuculose-1-phosphate aldolase; Streptococcus pneumonia glycerol phosphate oxidase; In water-d2; at 30℃; for 22h;pH 7;Enzymatic reaction; | General procedure: To a solution of DL-glycerol 3-phosphate magnesium salt (548.78 mg, 2.4 mmol) in 6.86 mL ddH2O was added <strong>[497-09-6]D-glyceraldehyde</strong> (or L-glyceraldehyde) (2 mL, 0.5 M, 1.0 mmol) at pH 7.0, glycerol phosphate oxidase saturated with FAD (final concentration 0.2 mg/mL), catalase (1000 U, 1.18 muL) and aldolase (final concentration 0.5 mg/mL). ddH2O was added to bring the total volume to 10 mL if necessary. The reaction mixture was shaken at 30 °C for 22 h and the reaction was monitored by TLC (developed by nBuOH/AcOH/H2O 2/1/1 (v/v/v) and stained with anisaldehyde sugar stain). The pH was then adjusted to pH ~5 with 6 N HCl and 11 muL acid phosphatase (18 U) was added and the mixture was shaken at 37 °C for 24 h. After cooling to rt., the pH was adjusted to 7.0 with 1 N NaOH and the mixture was diluted with methanol. The solution was filtered through Celite and washed with methanol. The filtrate was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (EtOAc/iPrOH/H2O 9/3/1 (v/v/v)) to afford a pale yellow syrup which was further purified by Bio gel P-2 column. The mixture of monosaccharides could be isolated by Ca2+ exchange resin column. The purification process using P-2 column or Ca2+ exchange resin column was performed with the same procedure we previously used. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 60.7% | With copper(II) oxide In water at 99.84℃; Inert atmosphere; | |
| 40.6% | With copper(II) oxide In water at 49.84℃; Inert atmosphere; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 85% | With copper(II) oxide In water at 199.84℃; for 0.5h; Inert atmosphere; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 27.6% | With Au NCs/TiO2; oxygen; potassium carbonate; molybdenum(VI) oxide at 89.84℃; for 5h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| Multi-step reaction with 7 steps 1.1: water; magnesium chloride / toluene / 0.5 h / 75 °C 1.2: 1 h / 75 °C 2.1: Jones reagent / acetone / 0 °C 3.1: diethyl ether / 0.17 h / 0 °C 4.1: sodium azide / DMF (N,N-dimethyl-formamide) / 1 h / 65 °C 5.1: triphenylphosphine / methanol / 2 h / 20 °C 5.2: 0.5 h / 20 °C 6.1: hydrogen / 20% Pd(OH)2 on carbon / methanol / 4 h / 20 °C 7.1: lithium hydroxide / tetrahydrofuran; methanol; water / 1 h / 0 - 20 °C 7.2: pH 2 |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With phosphomolybdic acid In water at 125℃; for 1h; | 2.3. Catalytic reaction General procedure: Hydrothermal reaction was performed in an autoclave reactor (BR-25, BERGHOF, Germany). In brief, required amounts of the substrate and catalyst were added into 7 mL of water and heated at the designatedtemperatures either in autogenous or aerobic condition. The reactionwas stopped by cooling down the reactor in an ice bath. Theremained cellulose was separated by filtration (ADVANTEC, 0.2 μm)and the filtrate was diluted with water before injected to HPLC. Thesamples were analyzed by using a Shimadzu Prominence HPLCequipped with a RID-10 A as well as a UV detector (210 nm) as describedin our previous study [32]. The yields of the products werecalculated based on carbon weight of the component and cellulose. Inthis context, carbon content of cellulose was determined by using anelemental analyzer (Vario EL cube elemental analyzer). |
[ 9005-80-5 ]
[ 57-48-7 ]
[ CAS Unavailable ]
[ 62512-19-0 ]
[ 470-69-9 ]
[ 13133-07-8 ]
[ 57-50-1 ]| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With water; Bacillus sp. 11/3 inulinase polyacrylamide/polyethylene glycol composite immobilised In aq. acetate buffer at 40℃; for 24h; Enzymatic reaction; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 26.8 %Chromat. | With [(1,2,3,4,5-pentamethyl-cyclopentadienide)Ir(α,α’-bipyridonate)]OH-; sodium hydroxide In acetonitrile at 150℃; Microwave irradiation; | 2.1. Conversion of C4-C6 sugars toward lactones General procedure: A certain amount of sugars was dissolved in the specific solvent and placed in a microwave-reaction tube (10 mL), and the dehydrogenation catalyst was added subsequently. For the conversion of C5/C6 sugars, additional NaOH (OH-/substrate molar ratio = 0-0.25) was added. The reaction temperature ranged from 80 °C to 180 °C, and the reaction last for 0-4 h |
Tags: D-Fructose | D(-)-Fructose | Endogenous Metabolite | 57-48-7 |
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Health hazards | |
| Code | Phrase |
| H300 | Fatal if swallowed |
| H301 | Toxic if swallowed |
| H302 | Harmful if swallowed |
| H303 | May be harmful if swallowed |
| H304 | May be fatal if swallowed and enters airways |
| H305 | May be harmful if swallowed and enters airways |
| H310 | Fatal in contact with skin |
| H311 | Toxic in contact with skin |
| H312 | Harmful in contact with skin |
| H313 | May be harmful in contact with skin |
| H314 | Causes severe skin burns and eye damage |
| H315 | Causes skin irritation |
| H316 | Causes mild skin irritation |
| H317 | May cause an allergic skin reaction |
| H318 | Causes serious eye damage |
| H319 | Causes serious eye irritation |
| H320 | Causes eye irritation |
| H330 | Fatal if inhaled |
| H331 | Toxic if inhaled |
| H332 | Harmful if inhaled |
| H333 | May be harmful if inhaled |
| H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
| H335 | May cause respiratory irritation |
| H336 | May cause drowsiness or dizziness |
| H340 | May cause genetic defects |
| H341 | Suspected of causing genetic defects |
| H350 | May cause cancer |
| H351 | Suspected of causing cancer |
| H360 | May damage fertility or the unborn child |
| H361 | Suspected of damaging fertility or the unborn child |
| H361d | Suspected of damaging the unborn child |
| H362 | May cause harm to breast-fed children |
| H370 | Causes damage to organs |
| H371 | May cause damage to organs |
| H372 | Causes damage to organs through prolonged or repeated exposure |
| H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
| Code | Phrase |
| H400 | Very toxic to aquatic life |
| H401 | Toxic to aquatic life |
| H402 | Harmful to aquatic life |
| H410 | Very toxic to aquatic life with long-lasting effects |
| H411 | Toxic to aquatic life with long-lasting effects |
| H412 | Harmful to aquatic life with long-lasting effects |
| H413 | May cause long-lasting harmful effects to aquatic life |
| H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
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