Purity | Size | Price | VIP Price | USA Stock *0-1 Day | Global Stock *5-7 Days | Quantity | |||||
{[ item.p_purity ]} | {[ item.pr_size ]} |
{[ getRatePrice(item.pr_usd, 1,1) ]} {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} |
{[ getRatePrice(item.pr_usd, 1,1) ]} | Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} {[ getRatePrice(item.pr_usd,1,item.mem_rate) ]} | {[ item.pr_usastock ]} | Inquiry - | {[ item.pr_chinastock ]} | Inquiry - |
* Storage: {[proInfo.prStorage]}
CAS No. : | 604-68-2 | MDL No. : | MFCD00064071 |
Formula : | C16H22O11 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | LPTITAGPBXDDGR-LJIZCISZSA-N |
M.W : | 390.34 | Pubchem ID : | 2723636 |
Synonyms : |
|
Num. heavy atoms : | 27 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.69 |
Num. rotatable bonds : | 11 |
Num. H-bond acceptors : | 11.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 84.42 |
TPSA : | 140.73 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | Yes |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -8.23 cm/s |
Log Po/w (iLOGP) : | 2.94 |
Log Po/w (XLOGP3) : | 0.63 |
Log Po/w (WLOGP) : | -0.37 |
Log Po/w (MLOGP) : | -0.6 |
Log Po/w (SILICOS-IT) : | 0.03 |
Consensus Log Po/w : | 0.53 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 2.0 |
Egan : | 1.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -1.93 |
Solubility : | 4.58 mg/ml ; 0.0117 mol/l |
Class : | Very soluble |
Log S (Ali) : | -3.16 |
Solubility : | 0.27 mg/ml ; 0.000691 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -0.57 |
Solubility : | 104.0 mg/ml ; 0.267 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 4.79 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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 |
---|---|---|
97.1% | With 4-methyl-morpholine; dmap; In dichloromethane; at 0 - 5℃; for 2h; | Take 1L three-port reaction bottle, install mechanical stirring, thermometer and constant pressure dropping funnel;200 ml of dichloromethane, 50 g (0.2775 mol) of d-glucose, 140.2 g (1.3875 mol) of N-methylmorpholine, 3.4 g (0.0275 mol) of DMAP were added to dissolve until dissolved; the temperature was lowered to 0-5 C, and 141.6 was slowly added. g (1.3875 mol) acetic anhydride, continue to react for 2 hours after completion; The solvent was distilled off at a high temperature, and 400 g of water was added to the reaction flask after completion, and the solid was stirred and precipitated, washed by filtration, and dried under vacuum to obtain 105.2 g of pentaacetylglucose, the yield was 97.1%; |
92% | With pyridine; dmap; at 0 - 20℃; for 20h; | To (2S, 3R,4S, 5S, 6R)-6-(hyd roxymethyl)tetrahydro-2H-pyran-2, 3,4, 5-tetraol 1 (50 g, 277.7 mmol) in pyridine (500 mL) at 0 C was added DMAP (339 mg, 2.777 mmol) and acetic anhydride (500 mL). The reaction mixture was further stirred at room temperature for 20 h. After completion of the reaction, the pyridine was evaporated under reducedpressure and the residue was diluted with water and extracted with CH2CI2 (thrice). The combined organic layer was dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude compound was purified by trituration with n-hexane to afford 100 g (92% yield) of compound 2 as off white solid.ELSD-Condition-1: [M-?-H] = 408.00; R = 2.88 mm1H NMR (400 MHz, CDCI3) 6: 6.33 (d, J = 3.91 Hz, I H), 5.47 (t, J = 10.03 Hz, I H), 5.07-5.17 (m, 2 H), 4.24-4.29 (m, I H), 4.08-4.15 (m, 2 H), 2.18 (5, 3 H), 2.09 (5, 3 H), 2.04 (5, 3 H), 2.03 (5, 3 H), 2.02 (5, 3 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | Stage #1: D-glucose; acetic anhydride With pyridine at 0 - 20℃; for 1h; Inert atmosphere; Stage #2: With dmap at 20℃; for 6h; Inert atmosphere; | 1 4.2.1. Fujihira's pathway To a solution of D-glucose 2 (3.00 g, 16.6 mmol) in dry pyridine(33 mL) at 0 C under a nitrogen atmosphere was slowly addedacetic anhydride (31.5 mL, 333 mmol). The reaction mixture wasstirred at 0 C for 1 h before a catalytic amount of DMAP (200 mg,1.67 mmol) was added. As the reaction mixture was allowed toreach rt, it became slightly exothermic. After 6 h, the clear yellowmixture was slowly poured into rapidly stirred ice-water (125 mL),giving a sticky solid. After EtOAc extraction (3 45 mL), evaporationof the solvent and co-evaporations with dry toluene(3 20 mL), peracetylated glucose was obtained as a yellow solid(5.84 g, 90%). A solution of pentaacetyl-D-glucopyranose 3 (1.12 g,2.9 mmol) in DCM (20 mL) was stirred in an ice bath while HBr/HOAc (6 mL, 45 wt%) was added drop-wise. After an hour, the solutionwas washed with ice-water and cold saturated NaHCO3 solution,dried over MgSO4 and concentrated to leave the glucosylbromide 4 as a pale yellow oil (1.03 g). The freshly prepared 4(1.03 g, 2.5 mmol) and N,N-dimethylthioformamide (230 mg,2.6 mmol) in the presence of 0.2 wt% H2O were stirred under anargon stream at 100 C for 5 min. Dry MeOH (20 mL) was addedafter cooling to rt, and the mixture was stirred for about 10 min(until the solid dissolved). The solvent was evaporated underreduced pressure, and the precipitated product was separated andpurified by flash column chromatography on silica gel eluting with66% hexane/EtOAc and then hexane:DCM:MeOH (25:24:1). The products were 2,3,4,6-tetra-O-acetyl-b/a-D-glucopyranosyl thiols(650 mg, 72%), ratio a (1):b (5) 1:1 (by NMR) as a colourless syrup. |
83% | at 28 - 32℃; for 0.116667h; | |
82.37% | With zinc(II) chloride at 60 - 100℃; for 4h; | 30.19 g of ZnCl2 was added to 600 mL of acetic anhydride, heated to 60 ° C, and the heating was stopped after the ZnCl 2 was completely dissolved. 100 g of glucose was added in batches and the temperature was controlled to not exceed 60 ° C. After the addition was completed, the mixture was heated to 100 ° C for 4 h.The temperature was lowered to room temperature, and the reaction liquid was poured into 3000 mL of ice water, and a solid precipitated. After stirring for 2 h, filtration, the filter cake was washed with water, dried and then recrystallized with 50% ethanol (3 times volume, heated to 80 ° C and dissolved completely to room temperature), dried at 60 ° C for 12 h under reduced pressure to give 5-O-acetyl- α-D-glucose white solid 162.10 g, yield 82.37%. |
81% | With pyridine; dmap In N,N-dimethyl-formamide at 20℃; for 3h; | 1.1A (2R,3R,4S,5R,6R)-6-(acetoxymethyl)tetrahydro-2H-pyran-2,3,4,5-tetrayl tetraacetate (1) To a solution of D-glucose (CAS50-99-7, 36.04 g, 0.2 mol) in anhydrous DMF (80 mL) was added sequentially acetic anhydride (188 mL), pyridine (162 mL, 2 mol), and DMAP (1.22 g, 0.01 mmol). The reaction mixture was stirred at ambient temperature for 3 h and quenched by dilution with water. The aqueous phase was extracted with ethyl acetate (2×300 mL) and the organic phase was washed with 1 N HCl (2×150 mL) and water. The organic layer was washed with saturated aq NaCl, dried over MgSO4 and concentrated. Recrystalization of the crude product from ethanol (400 mL) gave [(2R,3R,4S,5R)-3,4,5,6-tetrakis(acetyloxy)oxan-2-yl]methyl acetate as a white solid (63 g, 81%) white solid. |
With perchloric acid; acetic acid | ||
With chlorosulphuric acid | ||
With pyridine at 0℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96.8% | With triethylamine In chloroform at 0 - 10℃; for 2h; | 6 Anhydrous glucose (0.20 mol, 36 g) and triethylamine (0.06 mol, 6.1 g) were added to chloroform solvent (300 g), the temperature was lowered, acetyl chloride (1.2 mol, 94 g) Finished, observed after the suspension of glucose dissolved, continue to maintain the temperature 0-10 for 2 hours.After completion of the reaction, the reaction mixture was slowly added to 350 ml of ice water. The chloroform layer was separated and washed successively with 150 ml of water, 150 ml of saturated sodium bicarbonate and 150 ml of water. The chloroform layer was separated, dried over anhydrous sodium sulfate and concentrated under reduced pressure A white solid, recrystallized from absolute ethanol once to afford 75.6 g of pentacetylglucose as a white crystalline solid in 96.8% yield, m.p. 131-132 ° C |
With pyridine; chloroform |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With hydrazine hydrate; acetic acid; In tetrahydrofuran; at 24 - 33℃; for 4h; | A solution of [(2R,3R,4S,5R)-3,4,5,6-tetrakis(acetyloxy)oxan-2-yl]methyl acetate (50 g, 128.1 mmol) in THF (150 mL) was treated with acetic acid (8.07 mL, 140.9 mmol) and hydrazine monohydrate (7.05 g, 140.9 mmol). The temperature of reaction mixture was slightly exothermic while addition of hydrazine (24 C. to 33 C.). The reaction mixture was stirred at ambient temperature for 4 h and extracted with ethyl acetate (400 mL). The organic phase was washed with water (300 mL), dried over MgSO4, and concentrated to give crude glucose tetraacetate as a off-white solid (43 g). Purification using a short pad of silica gel gave [(2R,3R,4S,5R)-3,4,5-tris(acetyloxy)-6-hydroxyoxan-2-yl]methyl acetate yield 33 g (74%). (Note: In a pilot reaction, this was used in the next step without further purification). |
69% | In methanol; | EXAMPLE 9 2,3,4,6-Tetra-O-acetyl-D-glucopyranose is obtained in 69% yield from 1,2,3,4,6-penta-O-acetyl-alpha-D-glucopyranose according to Procedure B, by carrying out the reaction for 3 hours, in methanol at 50 C. |
45% | In toluene; | EXAMPLE 8 2,3,4,6-Tetra-O-acetyl-D-glucopyranose is obtained in 45% yield from 1,2,3,4,6-penta-O-acetyl-alpha-D-glucopyranose according to Procedure A, by carrying out the reaction for 1.5 hours, in refluxing toluene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With hydrogen bromide; glacial acetic acid | |
98% | Stage #1: 1,2,3,4,6-penta-O-acetyl-α-D-glucopyranoside With hydrogen bromide; glacial acetic acid Stage #2: at 0 - 20℃; for 2h; | |
95% | With acetic anhydride; phosphorus tribromide In lithium hydroxide monohydrate at 0℃; for 1h; |
91.7% | With black phosphorus; hydrogen bromide; bromine In acetic anhydride at 40 - 50℃; for 1h; | |
90% | With hydrogen bromide; glacial acetic acid In dichloromethane at 0 - 20℃; | |
90% | With hydrogen bromide; glacial acetic acid In dichloromethane at 0 - 20℃; Inert atmosphere; | 1-Bromo-1-deoxy-2,3,4,6-tetra-O-acetyl-α-D-glucopyranose: A solution of 1,2,3,4,6-Penta-O-acetyl-α-D-glucopyranose (500 mg, 1.28 mmol) in DCM (5 mL) was cooled to 0 °C with stirring under N2 atmosphere. 33% HBr in AcOH (2.6 mL) was added to the reaction mixture dropwise at 0 °C with stirring. The resulting reaction mixture was allowed to warm to room temperature. After 2 h the reaction mixture was diluted with water (5 mL) and DCM (5mL). The resulting mixture was extracted with DCM (3 x 5 mL). The organic extracts were combined, washed with saturated aqueous NaHCO3 (2 x 10 mL), water (2 x 10 mL), brine (1 x 15 mL), dried over anhydrous MgSO4, and concentrated to provide pure product as a white solid (473 mg, 90%). The spectroscopic data was consistent with that previously reported.18 |
89% | With hydrogen bromide; glacial acetic acid In dichloromethane at 0℃; for 4h; | 2 Step-2: Synthesis of (2R,3R,4S,5R,6R)-2-(acetoxymethyl)-6-bromotetrahydro-2H-15 pyran -3,4,5-triyl triacetate (3) To (2R, 3R,4S,5R, 6R)-6-(acetoxymethyl)tetrahydro-2H-pyran-2, 3,4, 5-tetrayl tetraacetate 1 (25 g, 64.04 mmol) in CH2CI2 (500 mL) at 0 °C was added 33% solution of HBr in acetic acid (250 mL) and stirred for 4 h. After completion of the reaction, the reactionmixture was poured over ice and the organic layer was separated and washed with water (400 mL) followed by saturated NaHCO3 (200 mL x 2). The combined organic layer was dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude compound was purified by silica gel column chromatography eluting with 0-50% ethyl acetate in n-hexane to afford 24 g (89%yield) of compound 3 asoff white solid.1H NMR (400 MHz, CDCI3): 6.61 (d, J = 3.91 Hz, I H), 5.56 (t, J = 9.54 Hz, I H), 5.17 (t, J= 9.78 Hz, I H), 4.84 (dd, J = 3.91, 10.27 Hz, I H), 4.28 -4.36 (m, 2 H), 4.10 -4.16 (m, I H), 2.10 (5, 3 H), 2.10 (5, 3 H), 2.06 (5, 3 H), 2.04 (5, 3 H). |
85% | With hydrogen bromide; glacial acetic acid In dichloromethane at 0 - 20℃; for 2h; | |
83% | With hydrogen bromide In dichloromethane; glacial acetic acid at 20℃; for 2h; | |
82% | With hydrogen bromide; glacial acetic acid In dichloromethane Inert atmosphere; | |
81.6% | With hydrogen bromide; glacial acetic acid In dichloromethane at 0 - 10℃; for 2h; | 1.1; 2.1; 3.1; 4.1 Take 1L three-neck reaction flask, install mechanical stirring, thermometer and constant pressure dropping funnel, add 80g (0.2050mol) of pentaacetyl glucose in 200ml of dichloromethane, cool down to 0 ~ 10 °C, slowly add 30% of hydrobromic acid acetic acid solution 196g (0.7187mol), After the completion of the reaction, the reaction was carried out for 2 hours, and 350 g of water was slowly added thereto, and the mixture was allowed to stand for separation. The aqueous phase was extracted with 250 ml of dichloromethane, and the organic phase was combined. The organic phase was washed with sodium hydrogen carbonate solution and brine, dried over anhydrous sodium sulfate and filtered. The filtrate is distilled off under reduced pressure to remove dichloromethane, and the remaining solid is added to 300 g of absolute ethanol to dissolve at a temperature, then cooled and crystallized, and filtered. Drying under reduced pressure gave 68.9 g of white bromotetraacetyl glucose in a yield of 81.6%. |
76% | With trimethylsilyl bromide In toluene at 80℃; for 5h; | |
76% | With hydrogen bromide In lithium hydroxide monohydrate; glacial acetic acid at 20℃; for 0.25h; diastereoselective reaction; | |
70% | With hydrogen bromide; acetic anhydride; glacial acetic acid at 0 - 20℃; for 15h; Inert atmosphere; | |
With hydrogen bromide In glacial acetic acid Ambient temperature; | ||
With trimethylsilyl bromide In dichloromethane | ||
With hydrogen bromide In glacial acetic acid | ||
Stage #1: 1,2,3,4,6-penta-O-acetyl-α-D-glucopyranoside With black phosphorus; bromine In acetic anhydride at 25℃; Stage #2: With lithium hydroxide monohydrate at 30℃; for 13h; | ||
With triethylsilane; carbon tetrabromide; palladium (II) chloride In dichloromethane at 20℃; for 2h; | ||
With hydrogen bromide; glacial acetic acid In dichloromethane at 0 - 25℃; for 3.5h; | ||
With hydrogen bromide In dichloromethane; glacial acetic acid at 0 - 20℃; for 18h; | 62 [00169] 1, 2,3, 4, 6-penta-0-acetyl-a-D-glucopyranose (1.0 g, 2.60 mmol) was dissolved in 20 mL of dichloromethane and 1.90 mL of hydrobromic acid (33% in acetic acid) at 0 °C, and the reaction was stirred while warming to room temperature. TLC (40% ethyl acetate-hexane) after 18 h showed complete consumption of the starting material and formation of a higher running spot. The reaction was slowly diluted with saturated sodium bicarbonate (25 mL), extracted into dichloromethane (2 x 100 mL), dried over sodium sulfate, filtered and concentrated to afford 2,3, 4, 6-tetra-0-acetyl-a-D- glucopyranosyl bromide which was used without purification. | |
With hydrogen bromide; glacial acetic acid | ||
With methanol; Acetyl bromide In glacial acetic acid at 20℃; for 24h; Inert atmosphere; | ||
With hydrogen bromide; glacial acetic acid | ||
With hydrogen bromide In glacial acetic acid | ||
With Acetyl bromide; glacial acetic acid In methanol at 15 - 25℃; for 24h; Darkness; Inert atmosphere; | 1 Synthesis of compound (8) To α,D-glucopyranose pentaacetate (1.00 g, 2.57 mmol), acetic acid (AcOH) (9.2 mL) was added under argon atmosphere. To the obtained solution, acetyl bromide (AcBr) (0.57 mL, 7.69 mmol) and methanol (MeOH) (0.15 mL, 3.70 mmol) were added, and the reaction solution was stirred at room temperature for one day under light-shielded conditions. [0133] The reaction solution after the stirring was concentrated, to give the unpurified targeted compound (the compound (8)) as a brown syrup-like liquid. Since the impurities can be removed in the next step, purification was not further performed herein. [0134] The NMR measurement result of the compound (8) was as described below. [0135] 1H NMR (400 MHz, CDCl3) δ2.03 (s, 3H), 2.05 (s, 3H), 2.10 (s, 3H), 2.10 (s, 3H), 4.13 (dd, J1 = 2.0 Hz, J2 = 14.4 Hz, 1H), 4.29 (ddd, J1 = 6.3 Hz, J2 = 5.4 Hz, J3 = 1.5 Hz, 1H), 4.33 (dd, J1 = 11.5 Hz, J2 = 3.9 Hz, 1H), 4.83 (dd, J1 = 10.0 Hz, J2 = 3.9 Hz, 1H), 5.18 (t, J = 9.8 Hz, 1H), 5.56 (t, J =9.8 Hz, 1H), 6.61 (d, J =3.9 Hz, 1H). | |
With hydrogen bromide; acetic anhydride In lithium hydroxide monohydrate for 3h; Cooling with ice; | 2.1. Terpene-β-D-glucopyranosides standards synthesis Four terpene alcohols: geraniol, nerol, citronellol and myrtenol were purchased form Sigma-Aldrich (Pozna, Poland) in the highest available purity grade. These standards were used to synthesize -d-glucopyranosides for model experiment. -d-glucose pentaacetate, acetic anhydride, hydrogen bromide, chloroform, dichloromethane, toluene, ethyl acetate, diethyl ether, methanol, anhydrous sodium sulfate Na2SO4, sodium methoxide, silica gel (SiO2 60, 40-63 μm), silver oxide Ag2O, Dowex 80H+ were purchased from Sigma Aldrich (Pozna, Poland). Glycosides were synthesized using general Koenigs-Knorr method with silver oxide against silver carbonate. The method is based on protecting hydroxyl groups in glucose by acetylation in acetic acid anhydride, and specific bromination. As a result tetra-O-acetobromo-α-d-glucose is formed. In a result of reaction with terpene alcohols, -d-glycoside is formed in anhydrous environment with Ag2O. Pentaacetate-α-d-glucose (2 g) was mixed with 20 ml of HBr and 5 ml of acetic anhydride in ice cooled round bottom flask for 3 h. After reaction products were dissolved in 50 ml of chloroform and washed with 4 portions of water (100 ml each). Organic layer was separated and dried over anhydrous sodium sulfate and evaporated in rotary evaporator. Acetylated glucose bromide was crystallized from 5 ml of diethyl ether (addition of petroleum ether - 1 ml if necessary). Product was dried for 1 h on glass funnel in vacuum flow and stored in argon in brown colored vial at -18 °C. Freshly prepared acetobromo-α-d-glucose (2 g) was mixed with terpene alcohol (5.6 g) in a presence of Ag2O (1.5 g) in freshly distilled and dried ethyl ether (50 ml) for 220 h in room temperature in darkness. Bromide was monitored using TLC (toluene: ethyl acetate 2:1, RF = 0.35). After reaction termination 20 ml of chloroform was added and reaction mixture was filtered using Büchner funnel. Filtrate was evaporated and a syrup containing geranyl glycoside was diluted three times in a mixture of toluene: ethyl acetate (4:1). Glycoside was purified using column chromatography (SiO2 60, 40-63 μm, 100 g) using toluene: ethyl acetate (4:1, v:v; RF = 0.42). Fractions containing glycoside were combined, evaporated and freeze-dried. White crystals of glycoside (1 g) were mixed in 0.4 N sodium methoxide (5 ml) until the disappearance of substrate (monitoring on TLC using chloroform: methanol (4:1, v:v), RF = 0.40). After reaction termination an excess of Dowex 80H+ was added to provide neutral pH. After filtration and evaporation the colored syrup was diluter three times with a mixture of chloroform:methanol (4:1, v:v) and purified on the SiO2 column described earlier using chloroform-methanol (4:1, v:v) for elution. Fractions containing glycoside were combined, concentrated in rotary evaporator and lyophilized (white powder). The same procedure was used for all terpene alcohols and also for the deuterated analog of geraniol. NMR analysis was performed to confirm obtained glycosides structures. | |
With hydrogen bromide; glacial acetic acid In dichloromethane at 0 - 20℃; for 6h; Inert atmosphere; | ||
With Acetyl bromide; glacial acetic acid In methanol at 15 - 25℃; for 18h; Inert atmosphere; | 1-1 Synthesis of compound (1-c) Under an argon atmosphere, to acetic acid (30.7 mL) solutionof shielded ice-cooled compound (1-a) 4.00 g (10.3 mmol) which is a startingmaterial, acetyl bromide 2.65 mL (35.8 mmol), methanol (MeOH) 0.55 mL (13.6mmol) were added sequentially. After stirring for 18 hours at room temperature,while heating to 80 ° C under a reduced pressure, low boiling point compoundwas distilled off to obtain a crude product of Compound (1-b). The resultingcrude product was used in the next reaction without any further purification.Under an argon atmosphere, to methylene chloride (400 mL)solution of the above crude product which is ice-cooled, sodium sulphate 14.6 g(103 mmol), diethylene glycol (diethyleneglycol) 10.0 mL (105 mmol) weresequentially added, and stirred at room temperature for 15 minutes. Theresulting solution was cooled again with ice, then silver carbonate 5.89 g(21.4 mmol) was added, and stirred at room temperature for 20 hours. From theresulting solution, insoluble components in methylene chloride were removed by suction filtration. After the filtrate was washed successively with water,saturated brine, it was dried with anhydrous sodium sulfate. the solvent wasevaporated under reduced pressure from the resulting solution, to give thecrude product. | |
With hydrogen bromide; glacial acetic acid | ||
With phosphorus tribromide In lithium hydroxide monohydrate at 0 - 20℃; for 2h; | 2,3,4,6-tetra-O-acetyl-1-α-D-Glucosyl bromide (3) Phosphorus bromide (32 mL) was added slowly to the mixture of compound 2 from last step at 0 °C and followed by addition of 16 mL water. After the solution was stirred at room temperature for 2 h, 150 mL dichloromethane was added. Then the mixture was slowly poured into 200 mL ice-water with stirring. The organic layer was separated and washed by saturated sodium hydrogen carbonate (100 mL*3) and brine (200 mL*3), then dried over anhydrous sodium sulfate overnight and filtered. Filtrate was concentrated in vacuum to give 3 as apale yellow oil (105 g, 94 %). | |
1.03 g | With hydrogen bromide; glacial acetic acid In dichloromethane for 1h; Cooling with ice; | 1 4.2.1. Fujihira's pathway To a solution of D-glucose 2 (3.00 g, 16.6 mmol) in dry pyridine(33 mL) at 0 C under a nitrogen atmosphere was slowly addedacetic anhydride (31.5 mL, 333 mmol). The reaction mixture wasstirred at 0 C for 1 h before a catalytic amount of DMAP (200 mg,1.67 mmol) was added. As the reaction mixture was allowed toreach rt, it became slightly exothermic. After 6 h, the clear yellowmixture was slowly poured into rapidly stirred ice-water (125 mL),giving a sticky solid. After EtOAc extraction (3 45 mL), evaporationof the solvent and co-evaporations with dry toluene(3 20 mL), peracetylated glucose was obtained as a yellow solid(5.84 g, 90%). A solution of pentaacetyl-D-glucopyranose 3 (1.12 g,2.9 mmol) in DCM (20 mL) was stirred in an ice bath while HBr/HOAc (6 mL, 45 wt%) was added drop-wise. After an hour, the solutionwas washed with ice-water and cold saturated NaHCO3 solution,dried over MgSO4 and concentrated to leave the glucosylbromide 4 as a pale yellow oil (1.03 g). The freshly prepared 4(1.03 g, 2.5 mmol) and N,N-dimethylthioformamide (230 mg,2.6 mmol) in the presence of 0.2 wt% H2O were stirred under anargon stream at 100 C for 5 min. Dry MeOH (20 mL) was addedafter cooling to rt, and the mixture was stirred for about 10 min(until the solid dissolved). The solvent was evaporated underreduced pressure, and the precipitated product was separated andpurified by flash column chromatography on silica gel eluting with66% hexane/EtOAc and then hexane:DCM:MeOH (25:24:1). The products were 2,3,4,6-tetra-O-acetyl-b/a-D-glucopyranosyl thiols(650 mg, 72%), ratio a (1):b (5) 1:1 (by NMR) as a colourless syrup. |
With hydrogen bromide; glacial acetic acid In dichloromethane at 0℃; for 0.666667h; | 1.1 Example 1 Add 65.2 g (1.1 eq) of sodium acetate to 700 mL of acetic anhydride.Heated at 140 ° C,Add 130.46g (724.20mmol, 1eq) to the reaction system in small portions.D-galactose (compound of formula 10),After joining,The reaction solution becomes clear,Continue to reflux for 10 minutes.Pour the hot solution into a beaker containing 4000 mL of ice water.Until the ice water melts.Add 1200 mL of methylene chloride to the mixed solution.The aqueous phase is then removed.The organic phase is ice water (3*4000mL),Wash with saturated aqueous sodium carbonate (4000 mL) and brine (4000 mL).Dry the organic phase with sodium sulfate,filter,Concentration under reduced pressure gave a crude yellow oil.The crude product was dissolved in a small amount of diethyl ether (about 250 mL).The precipitate was precipitated by successively adding petroleum ether (500 mL) and ethanol (2000 mL).The suspension is stored at 24 ° C for 2-3 hours.It was then stored at -20 ° C for 16 hours.It was then filtered to a white solid and washed with petroleum ether.Recrystallizing the solid in a small amount of hot ethanol,Store at room temperature for 16 hours.Finally the crystals were filtered and washed with cold ethanol and petroleum ether.Obtaining penta-O-acetyl β-D-galactopyranoside,At 0 ° C,Dissolving penta-O-acetyl β-D-galactopyranosine in dichloromethane,A solution of hydrobromic acid in acetic acid (33% w/w, 11 eq),The addition is completed within 10 minutes.The reaction mixture was stirred at 0 ° C for 30 minutes.It was then stirred at room temperature until the reaction was complete (about 3 hours).The mixture was diluted with 10 mL of dichloromethane.Wash twice with 30 mL of saturated sodium carbonate solution.Wash once with 200 mL of deionized water.The organic phase was dried over sodium sulfate and concentrated.2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl bromide is obtained.The obtained 2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl bromide is hydrolyzed under acidic conditions.Obtaining 124.97g of the compound of formula 11;Purity 99.2%;Yield 71%; | |
With hydrogen bromide; glacial acetic acid at 20℃; for 3h; Darkness; | 1 Reference Example 1 Preparation of tetra-O-acetyl-α-D-glucosyl Bromide (TAGluB) TAGluB used in the following Examples and Comparative Examples was prepared. 20 g of penta-O-acetyl-α-D-glucopyranose and 100 g of hydrogen bromide acetic acid solution (25%) were weighed, mixed, and then stirred at room temperature under shading for 3 hours. The reaction product was extracted with ethyl acetate, the extract was neutralized with a saturated aqueous solution of sodium bicarbonate, salted out with saturated saline, and dried with magnesium sulfate in order to produce TAGluB. | |
With hydrogen bromide; glacial acetic acid In dichloromethane for 2h; | ||
With hydrogen bromide; glacial acetic acid In dichloromethane | ||
With red phosphorus; bromine In lithium hydroxide monohydrate at 15 - 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With boron trifluoride diethyl etherate In dichloromethane for 5h; Ambient temperature; | |
2.45 g (61%) | With trifluoroborane diethyl ether In dichloromethane | 1.1 Example 1 (1) Boron trifluoride etherate (4 ml, 32 mmol) was added to a solution of 1,2,3,4,6-penta-O-acetyl-α-D-glucopyranoside (2.5 g, 8.0 mmol) and 8-methoxycarbonyl octanol (3.0 g) in methylene chloride (30 ml). The mixture was stirred at room temperature for 5 hr. The reaction solution was washed with water and dried over magnesium sulfate. After filtration, the filtrate was concentrated to dryness under the reduced pressure. The oil thus obtained was purified by column chromatography on silica gel (toluene-acetone (9: 1)) to give 2.45 g (61%) of 8-methoxycarbonyloctyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside. [α]D17+3.73° (c = 1.42, chloroform) 1H-NMR (CDCl3) δ: 1.56 (8H, s), 1.57-1.63 (4H, m), 2.01 (3H, s), 2.02 (3H, s), 2.04 (3H, s), 2.09 (3H, s), 2.30 (2H, t, J = 7.6 Hz), 3.46 (1H, dt, J = 9.5, 6.8 Hz), 3.67 (3H, s), 3.69 (1H, ddd, J = 2.4, 4.6, 9.8 Hz, H-5), 3.86 (1H, dt, J = 9.5, 6.4 Hz), 4.15 (1H, dd, J = 12.4, 2.4 Hz, H-6), 4.28 (1H,dd, J = 12.4, 4.6 Hz, H-6), 4.49 (1H, d, J = 8.1 Hz, H-1), 4.98 (1H, dd, J = 9.5, 8.1 Hz, H-2), 5.09 (1H, dd, J = 9.8, 9.5 Hz, H-4), 5.20 (1H, dd, J = 9.5, 9.5 Hz, H-3) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: HBr / acetic acid / Ambient temperature 2: 43 percent / aq. NaOH / acetone / 7 h / Ambient temperature 3: 6mM methanolic MeONa / 5 h / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: 91.7 percent / red phosphorus, bromine, aq. HBr / acetic anhydride / 1 h / 40 - 50 °C 2: 95 percent / acetone / 0.5 h / Heating 3: 96 percent / K2CO3, NaHSO3 / acetone; H2O / Ambient temperature 4: NaOH / methanol / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With acetic anhydride In xylene at 90 - 105℃; for 17h; | 5 EXAMPLE 5 To a reactor were fed 153.0 g (0.849 mol) of glucose (hereinafter referred to as "GLC"), 459 g of xylene, and 1.53 g (one percent by weight relative to the GLC) of sodium acetate as a catalyst, and then 520.3 g (5.09 mol) of acetic anhydride was added dropwise over a period of three hours at a temperature of 90 C to 95 C. After the dropwise addition, the reaction was maintained at 105 C for 14 hours. The reaction quantitatively proceeded. The conversion rate of the GLC was 100%. The resulting glucose pentaacetate was a mixture of α-PAG and β-PAG, the ratio of α-PAG to β-PAG being 2:8. After the reaction, acetic acid formed by the acylation in a reactor equipped with a distillation column having three to five theoretical plates was azeotropically distilled with the xylene. In fact, 1071 g of xylene was added to the mixture subjected to the acylation, and then 1546 g of an azeotropic mixture of xylene and acetic acid was distilled off at 45 C to 55 C under reduced pressure. The acetic acid in the distillate was 260.7. Only 0.1% of acetic acid relative to the amount of acetic acid formed by the acylation remained in the reaction mixture containing prepared PAG in the reactor. | |
Multi-step reaction with 3 steps 1.1: pyridine; dmap / 4 h / 20 °C 1.2: TS-1 / 0.5 h / 0 °C 1.3: 1 h / 20 °C 2.1: water; ruthenium trichloride; sodium periodate; cerium(III) chloride heptahydrate / dichloromethane / 0 - 20 °C 3.1: pyridine; dmap / dichloromethane / 1 h / 0 - 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With silica gel; In methanol; dichloromethane; at 110℃; for 0.05h;Microwave irradiation; | General procedure: Microwave Synthesis (Method A) A mixture of 2(1H)-pyridones 1a-d or 6a-c (10 mmol) and 1,2,3,4,6-penta-O-acetyl-alpha-D-glucopyranose (11 mmol, 4.29 g) or 1,2,3,5-tetra-O-acetyl-alpha-D-ribofuranose (11 mmol, 3.51 g), respectively, were dissolved in a mixture of methylene chloride/methanol (80/20); then 1.0 g of silica gel (200-400mesh) was added and then the solvent was removed by evaporation. The dried residue was transferred into a 10 mL vial and irradiated for 2-3 minutes using CEM Microwave (200 W) system at 110C constant temperature.The product was purified using column chromatography in MeOH (0-2%) CHCl3 to afford the products 4a-d, 9a-c, and 12. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: hydrogen bromide; acetic acid / dichloromethane / 2 h / 0 - 10 °C 2.1: isopropylmagnesium chloride / tetrahydrofuran / 2 h / 0 - 10 °C / Inert atmosphere 2.2: 2 h / -15 - 10 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: acetonitrile / 12 h / 20 °C 2: potassium carbonate / dichloromethane / 6 h / 20 °C / Inert atmosphere 3: boron trifluoride diethyl etherate / dichloromethane / 9 h / 20 °C / Inert atmosphere 4: sodium methylate / methanol |
Precautionary Statements-General | |
Code | Phrase |
P101 | If medical advice is needed,have product container or label at hand. |
P102 | Keep out of reach of children. |
P103 | Read label before use |
Prevention | |
Code | Phrase |
P201 | Obtain special instructions before use. |
P202 | Do not handle until all safety precautions have been read and understood. |
P210 | Keep away from heat/sparks/open flames/hot surfaces. - No smoking. |
P211 | Do not spray on an open flame or other ignition source. |
P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
P223 | Keep away from any possible contact with water, because of violent reaction and possible flash fire. |
P230 | Keep wetted |
P231 | Handle under inert gas. |
P232 | Protect from moisture. |
P233 | Keep container tightly closed. |
P234 | Keep only in original container. |
P235 | Keep cool |
P240 | Ground/bond container and receiving equipment. |
P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
P242 | Use only non-sparking tools. |
P243 | Take precautionary measures against static discharge. |
P244 | Keep reduction valves free from grease and oil. |
P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
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 |
Sorry,this product has been discontinued.
Home
* Country/Region
* Quantity Required :
* Cat. No.:
* CAS No :
* Product Name :
* Additional Information :