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Chemical Structure| 22860-23-7

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Product Details of [ 22860-23-7 ]

CAS No. :22860-23-7
Formula : C12H14O8
M.W : 286.23
SMILES Code : CC(OC[C@@H]1[C@@H](OC(C)=O)C=C(OC(C)=O)C(O1)=O)=O

Safety of [ 22860-23-7 ]

Application In Synthesis of [ 22860-23-7 ]

* 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.

  • Downstream synthetic route of [ 22860-23-7 ]

[ 22860-23-7 ] Synthesis Path-Downstream   1~6

  • 1
  • [ 67-56-1 ]
  • [ 22860-23-7 ]
  • [ 6338-41-6 ]
  • [ 36802-01-4 ]
YieldReaction ConditionsOperation in experiment
16%; 69% at 22℃; for 72h; General procedure: Starting from, D-glucono-5-lactone (1.01 g), acetic anhydride (8 ml_), iodine (6.8 mg) and NaOAc (533 mg), compound 1 was produced as in method 2 of EXAMPLE 1. The resulting crude syrup of compound 1 was dissolved in 10 mL MeOH and to this acetyl chloride (50 pL, 0.12 eq) was added. After stirring for 3 days TLC indicated full conversion, the reaction mixture was concentrated and purified by column chromatography (1 : 6 acetone/toluene) to yield compound 2 as yellowish oil (612 mg, 69 %). bp 121-124 C (2.1-2.4*101mbar), *H NMR (500 MHz, CDCb) d 7.13 (d, J33A = 3.5 Hz, 1H, H3), 6.41 (dt, J = 0.8 Hz, 1H, H4), 4.68 (d, J3CH2,OH = 6.2 Hz, 2H,CH2hydroxymethyi); 3 8g (S; 3H;CH3ester), 2.14 (t, 1H, OH).13C NMR (126 MHz, CDCb) d 159.3 (COester), 158.4 (C5), 144.2 (C2), 119.0 (C3), 109.6 (C4), 57.7 (CHz^^y^y'), 52.1 (CH3ester)· Identical to reported NMR3' and13C NMR3spectra.The yield in the present example is the total yield of HMMF over three steps stemming from glucono-lactone.
  • 2
  • [ 22860-23-7 ]
  • [ 64-17-5 ]
  • [ 6338-41-6 ]
  • 2,4-di-O-acetyl-D-erythro-hex-2-enono-1,5-lactone [ No CAS ]
  • 2-O-acetyl-D-erythro-hex-2-enono-1,5-lactone [ No CAS ]
  • [ 76448-73-2 ]
YieldReaction ConditionsOperation in experiment
17%; 26 mg; 56 mg; 34% With acetyl chloride; at 22℃; for 72h; A crude syrup of 1 (1.180 g) was dissolved in 10 mL Absolut EtOH and to the resulting mixture was added AcCI (58 pL, 0.2 eq) at 22 C. After 3 days, TLC analysis indicated full conversion of the starting material and the reaction mixture was concentrated, dissolved in acetone and concentrated on silica. This material was purified by column chromatography (1 : 51: 34: 6 acetone/toluene) to give the title compound 3 (240 mg, 34 %). *H NMR (500 MHz, CDCb) d 7.11 (d, J = 3.5 Hz, 1H, H3), 6.40 (d, J = 3.5 Hz, 1H, H2), 4.67 (s, 2H, H6), 4.35 (q, J = 7.1 Hz, 2H, HllEt), 2.24 (br s, 1H, H70H), 1.36 (t, J = 7.1 Hz, 3H, H12Et).13C NMR (126 MHz, CDCb) d 158.9 (Cl), 158.3 (C8C0), 144.5 (C4), 118.8 (C3), 109.5 (C2), 61.2 (CllEt), 57.7 (C6), 14.5 (C12Et). HRMS (ESP-TOF) m/z for C8HioNa04+(MNa+) calculated : 193.0471; found : 193.0478. Besides 3, the following was also isolated, 5-(hydroxymethyl)furan-2-carboxylic acid (98 mg, 17 %), 2, 4-di-0-acetyl-D-erythro-hex-2-enono-l, 5-lactone (26 mg) and 2-0-acetyl-D-erythro-hex-2-enono-l, 5-lactone (56 mg).
  • 3
  • [ 22860-23-7 ]
  • [ 71-36-3 ]
  • [ 6338-41-6 ]
  • butyl 5-(hydroxymethyl)furan-2-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
26%; 37% With acetyl chloride; at 22℃; for 48h; A crude syrup of 1 (516 mg) was dissolved in 5.0 mL 1-butanol and to the resulting mixture was added AcCI (60 pL) at 22 C, the mixture was initially heated to allow the starting material to fully dissolve. After 2 days TLC analysis indicated full conversion of the starting material and the reaction mixture was concentrated, dissolved in acetone and concentrated on silica. This material was purified by column chromatography (1 : 61 : 5 acetone/toluene) to give 5- (hydroxymethyl)furan-2-carboxylic acid (65 mg, 26 %) and the title compound 4 (133 mg, 37 %).*H NMR (500 MHz, CDCb) d 7.11 (d, J = 3.5 Hz, 1H, H3), 6.41 (d, J = 3.4 Hz, 1H, H2), 4.67 (d, J = 5.3 Hz, 2H, H6), 4.30 (t, J = 6.7 Hz, 2H, HllnBu), 2.11 (br t, J = 5.3 Hz, 1H, H70H), 1.72 (p, J = 6.8 Hz, 2H, H12nBu), 1.44 (h, J = 7.4 Hz, 2H, H13nBu), 0.96 (t, J = 7.4 Hz, 3H, H14nBu).13C NMR (126 MHz, CDCb) d 159.0 (Cl), 158.3 (C8C0), 144.5 (C4), 118.7 (C3), 109.5 (C2), 65.0 (CllnBu), 57.8 (C6), 30.9 (C12nBu), 19.3 (C13nBu), 13.9 (C14nBu). HRMS (ESP-TOF) m/z for CioHi4NaC>4+(MNa+) calculated : 221.0784; found : 221.0792.
  • 4
  • [ 22860-23-7 ]
  • [ 78-92-2 ]
  • [ 6338-41-6 ]
  • sec-butyl 5-(hydroxymethyl)furan-2-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
29%; 15% With acetyl chloride; at 22℃; for 48h; A crude syrup of 1 (476 mg) was dissolved in 5.0 mL 2-butanol and to the resulting mixture was added AcCI (60 pL) at 22 C, the mixture was initially heated to allow the starting material to fully dissolve. After 2 days, with little conversion, the reaction mixture was heated to 70 C overnight and TLC analysis indicated full conversion of the starting material. The mixture was concentrated, dissolved in acetone and concentrated on silica. This material was purified by column chromatography (1 : 61 : 5 acetone/toluene) to give 5-(hydroxymethyl)furan-2- carboxylic acid (69 mg, 29 %) and the title compound 5 (49 mg, 15 %). *H NMR (500 MHz, CDCb) d 7.10 (d, J = 3.4 Hz, 1H, H3), 6.40 (d, J = 3.4 Hz, 1H, H2), 5.06 (h, J = 6.3 Hz, 1H, HllsBu), 4.67 (s, 2H, H6), 1.77 - 1.57 (m, 2H, H12sBu), 1.31 (d, J = 6.3 Hz, 3H, H14sBu), 0.95 (t, J = 7.5 Hz, 3H, H13sBu).13C NMR (126 MHz, CDCb) d 158.6 (Cl), 158.0 (C8C0), 144.7 (C4), 118.3 (C3), 109.4 (C2), 73.2 (CllsBu), 57.6 (C6), 28.9 (C12sBu), 19.6 (C14sBu), 9.7 (C13sBu). HRMS (ESP-TOF) m/z for CioHi4NaC>4+(MNa+) calculated : 221.0784; found : 221.0792.
  • 5
  • [ 22860-23-7 ]
  • [ 107-18-6 ]
  • [ 6338-41-6 ]
  • allyl 5-(hydroxymethyl)furan-2-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
19%; 25% With acetyl chloride; at 22℃; for 48h; A crude syrup of 1 (505 mg) was dissolved in 5.0 mL allyl alcohol and to the resulting mixture was added AcCI (60 pL) at 22 C. After 2 days, TLC analysis indicated full conversion of the starting material. The mixture was concentrated, dissolved in acetone and concentrated on silica. This material was purified by column chromatography (1 : 61 : 5 acetone/toluene) to give 5-(hydroxymethyl)furan-2-carboxylic acid (48 mg, 19 %) and the title compound 6 (82 mg, 25 %).*H NMR (500 MHz, CDCB) d 7.16 (d, J = 3.4 Hz, 1H, H3), 6.42 (d, J = 3.4 Hz, 1H, H2), 6.00 (ddt, J = 17.2, 10.5, 5.8 Hz, 1H, H12AN), 5.40 (dq, J = 17.2, 1.5 Hz, 1H, H13All trans), 5.29 (dq, J = 10.3, 1.3 Hz, 1H, H13AI| C/S), 4.80 (dt, J = 5.8, 1.4 Hz, 2H,H11AN), 4.68 (d, J = 5.7 Hz, 2H, H6), 2.03 (t, J = 6.3 Hz, 1H, H70H).13C NMR (126 MHz, CDCb) d 158.5 (2C, Cl, C8C0), 144.2 (C4), 131.9 (C12AN), 119.1 (C3), 119.0 (C13AN), 109.6 (C2), 65.7 (C11AN), 57.8 (C6). HRMS (ESP-TOF) m/z for CgHioNaO^ (MNa+) calculated : 205.0471; found : 205.0478.
  • 6
  • [ 22860-23-7 ]
  • [ 6338-41-6 ]
YieldReaction ConditionsOperation in experiment
D-glucono-6-lactone (20.5 g, 115 mmol) was suspended in acetic anhydride (56 mL, 0.59 mol) together with freshly washed Amberlite IR-120 (H) and stirred for 30 minutes at 60 C. The resulting clear mixture was filtered and NaOAc (10.7 g, 131 mmol) was added at 60 C, stirred overnight at 40 C and heated to 60 C, after 3 hours NMR indicates >95% conversion. The reaction mixture was cooled to room temperature, filtered and everything washed twice with 25 mL toluene then concentrated, this was suspended in 25 mL toluene, filtered, washed twice with 10 mL toluene and concentrated again to yield yellow syrup of compound 1. This was dissolved in 70 mL MeOH together with AcCI (0.82 mL, 11.5 mmol) and refluxed until TLC indicated full conversion. The mixture was cooled and 0.8 M HCI (22 mL) was added to the solution, this mixture was refluxed for 30 minutes and 10 mL of H20/MeOH mixture was distilled off. The mixture was further concentrated to give a black solid that was easily soluble in MeOH, NMR indicates that this crude product is ~95 % pure 5-(hydroxymethyl)furoic acid (HMFA), 7.*H NMR (500 MHz, MeOD) d 7.12 (d, J = 3.5 Hz, 1H, H3), 6.43 (d, J = 3.5 Hz, 1H, H4), 4.54 161.8 (Clc=0),160.5 (C5), 145.5 (C2), 120.0 (C3), 110.3 (C4), 57.4 (C6hydroxymethy')·
 

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