2-Deoxy-2,2-difluoro-D-ribofuranose-3,5-dibenzoate-1-methanesulfonate Chemical Properties

Boiling point:

588.4±50.0 °C(Predicted)

Density 

1.46

storage temp. 

2-8°C

Appearance

White to off-white Solid

2-Deoxy-2,2-difluoro-D-ribofuranose-3,5-dibenzoate-1-methanesulfonate Usage And Synthesis

Uses

2-Deoxy-2,2-difluoro-3,5-dibenzoate-1-methanesulfonate α-D-erythro-Pentofuranose is an impurity of Gemcitabine (G305028), a potential anticancer agent.

Synthesis

((2R,3R)-3-(Benzoyloxy)-4,4-difluoro-5-hydroxytetrahydrofuran-2-yl)methyl benzoate (4.14 g, 10.9 mmol) was dissolved in anhydrous dichloromethane (52 mL), anhydrous triethylamine (2.4 mL) was added and the solution was cooled to 0 °C. Methylsulfonyl chloride (1.23 mL, 15.8 mmol) was added slowly and dropwise with stirring. The reaction mixture was stirred at room temperature for 18 hours. Upon completion of the reaction, the mixture was transferred to a partition funnel and partitioned with methylene chloride (140 mL) and saturated sodium bicarbonate solution (56 mL). The organic phase was separated, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give an oily product as a mixture of isoheads (5.03 g, quantitative yield). The chemical shifts were analyzed by 19F NMR (CDCl3, 471 MHz) and were δ -107.770, -108.22, -120.65, -121.17, -122.21, -122.73, -123.76, -124.45.1H NMR (CDCl3, 500 MHz) data of the main isocaprolite (60%): δ 8.13-8.04 (m, 4H, benzoyl), 7.65-7.54 (m, 2H, benzoyl), 7.50-7.41 (m, 4H, benzoyl), 6.17 (d, J=5.6 Hz, 1H, H-1), 5.62 (dd, J1=4.2 Hz, J2=16.4 Hz, 1H, H-3), 4.91 (q, J= 3.9 Hz, 1H, H-4), 4.81-4.61 (m, 2H, H-5), 3.17 (s, 3H, CH3). 1H NMR (CDCl3, 500MHz) data of the minor isohead (40%): δ 8.13-8.04 (4H, m, benzoyl), 7.65-7.54 (m, 2H, benzoyl), 7.50-7.41 (m, 4H, benzoyl), 6.09 (d, J=6.4Hz, 1H, H-1), 5.98 (dt, J1 = 7.3 Hz, J2=15.0 Hz, 1H, H-3), 4.81-4.61 (m, 3H, H-4, H-5), 3.03 (s, 3H, CH3).13C NMR (CDCl3, 126 MHz) data: δ 40.09, 40.20 (CH3), 62.52, 63.08 (C-5), 69.61 (dd ), 71.04 (dd, J1C-F=15.7 Hz, J2C-F=26.0 Hz, C-3), 79.68, 79.75, 82.59 (C-4), 98.81 (dd, J1C-F=25.0 Hz, J2C-F=41.8 Hz, C-1), 99.52 (dd, J1C-F=25.0 Hz, J2C-F=41.8 Hz, C-1), 99.52 (dd, J1C-F=25.0 Hz, J2C-F=41.8 Hz C-1), 99.52 (dd, J1C-F=24.5Hz, J2C-F=46.3Hz, C-1), 120.61 (dd, J1C-F=253.5Hz, J2C-F=269.8Hz, C-2), 120.91 (dd, J1C-F=249.3Hz, J2C-F=276.3Hz, C-2) , 128.42, 128.58, 128.63, 128.70, 128.76, 128.79 (benzene ring), 129.18, 129.25 ('ipso' benzene ring), 129.76, 130.07, 130.14, 133.51, 133.63, 134.19, 134.26 (benzene ring), 164.89 , 165.03, 165.81, 165.90 (carbonyl).

References

[1] Synthesis, 1992, # 6, p. 565 - 570
[2] Bioorganic and Medicinal Chemistry, 2011, vol. 19, # 14, p. 4338 - 4345
[3] Patent: WO2009/61781, 2009, A1. Location in patent: Page/Page column 102-103
[4] Biochemistry, 2010, vol. 49, # 7, p. 1404 - 1417
[5] Patent: WO2005/95430, 2005, A1. Location in patent: Page/Page column 18

2-Deoxy-2,2-difluoro-D-ribofuranose-3,5-dibenzoate-1-methanesulfonate(134877-42-2)Related Product Information

• Deoxyribonuclease
• DEOXYRIBONUCLEIC ACID SODIUM SALT
• 3Epigemcitabine
• Cytosine
• Gemcitabine Impurity 21
• 2-Deoxy-2,2-difluoro-D-erythro-pentafuranous-1-ulose-3,5-dibenzoate
• b-D-ribofuranose, 2-deoxy-2,2-difluoro-
• Gemcitabine hydrochloride
• (R)-(+)-2,2-Dimethyl-1,3-dioxolane-4-carboxaldehyde
• Ethyl 3-(2,2-dimethyl-1,3-dioxolan-4-yl)-2,2-difluoro-3-hydroxypropionate
• 4-Amino-1-(2-deoxy-2,2-difluoro-a-D-erythro-pentofuranosyl)-2(1H)-pyrimidinone Hydrochloride
• Gemcitabine Impurity 10
• Gemcitabine Impurity 12
• α-D-erythro-Pentofuranose-2-deoxy-2,2-difluoro-3,5-dibenzoate
• DnaseⅠ
• DNA, SINGLE STRANDED, IMM. ON CELLULOSE, FROM CALF THYMUS*
• methanesulfonate
• 2-Deoxy-2,2-difluoro-D-ribofuranose-3,5-dibenzoate-1-methanesulfonate