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Chemical Structure| 680-15-9 Chemical Structure| 680-15-9

Structure of 680-15-9

Chemical Structure| 680-15-9

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Product Details of [ 680-15-9 ]

CAS No. :680-15-9
Formula : C3H3F3O4S
M.W : 192.11
SMILES Code : O=C(OC)C(F)(F)S(=O)(F)=O
MDL No. :MFCD00144316
InChI Key :GQJCAQADCPTHKN-UHFFFAOYSA-N
Pubchem ID :547667

Safety of [ 680-15-9 ]

GHS Pictogram:
Signal Word:Danger
Hazard Statements:H225-H314
Precautionary Statements:P280-P305+P351+P338-P310
Class:8(3)
UN#:2920
Packing Group:

Application In Synthesis of [ 680-15-9 ]

* 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 [ 680-15-9 ]

[ 680-15-9 ] Synthesis Path-Downstream   1~8

  • 1
  • [ 680-15-9 ]
  • [ 25391-60-0 ]
  • [ 99368-67-9 ]
YieldReaction ConditionsOperation in experiment
30% With copper(l) iodide; In N,N-dimethyl-formamide; at 70℃; for 19.0h; B. 2-Chloro-5-nitro-3-(trifluoromethyl)pyridineIn a schlenck tube, a mixture of <strong>[25391-60-0]2-chloro-3-iodo-5-nitropyridine</strong> (17.58 mmol, 5.00 g), methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (8.79 mmol, 1.12 ml) and CuI (2.64 mmol, 0.5 g) in DMF (30 ml) was heated at 7O0C for 3 hours under argon atmosphere. Methyl 2,2- difluoro-2-(fluorosulfonyl)acetate (4.40 mmol, 0.6 ml) was added and the mixture was heated at 7O0C for 16 hours. The solvent was evaporated and the crude mixture was extracted between ethyl acetate and water. The crude mixture was purified by chromatography over SiO2 eluting with hexane/DCM mixtures affording 1.19 g (yield 30percent) of the expected product.1H NMR (300 MHz, CDCI3) delta ppm: 8.82 (s, 1 H), 9.41 (s, 1 H). B. 2-ChIoro-5-nitro-3-(trifluoromethyl)pyridineIn a schlenk tube, a mixture of <strong>[25391-60-0]2-chloro-3-iodo-5-nitropyridine</strong> (17.58 mmol, 5.00 g), methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (8.79 mmol, 1.12 ml) and CuI (2.64 mmol, 0.5 g) in DMF (30 ml) was heated at 7O0C for 3 hours under argon atmosphere. Methyl 2,2- difluoro-2-(fluorosulfonyl)acetate (4.40 mmol, 0.6 ml) was added and the mixture was heated at 7O0C for 16 hours. The solvent was evaporated and the crude mixture was extracted between ethyl acetate and water. The crude mixture was purified by chromatography over SiO2 eluting with hexane/DCM mixtures affording 1.19 g (yield 30percent) of the expected product. delta 1H NMR (300 MHz, CDCI3): 8.82 (s, 1H), 9.41 (s, 1 H).
21% With copper(l) iodide; hydrogen; In N,N-dimethyl-formamide; at 70℃; for 19.0h; In a 100 mL round bottom flask, a mixture of <strong>[25391-60-0]2-chloro-3-iodo-5-nitropyridine</strong> (250 mg, 0.88 mmol), methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (0.06 mL, 0.44 mmol) and Copper(l) iodide (25 mg, 0.13 mmol) in dimethylformamide was heated at 70 °C for 3h under hydrogen atmosphere. Another 0.03 mL methyl 2,2-difluoro-2-(fluorosulfonyl)acetate was added and the mixture was heated at 70 °C for 16 h. The reaction mixture was cooled to room temperature, diluted with water and extracted with ethyl acetate. The organic layer was concentrated under reduced pressure to afford the crude which was purified by column chromatography to give 2-chloro-5-nitro-3-(trifluoromethyl)pyridine (41 mg, 21 percent).
21% With copper(l) iodide; hydrogen; In N,N-dimethyl-formamide; at 70℃; for 19.0h; In a 100 mL round bottom flask, a mixture of <strong>[25391-60-0]2-chloro-3-iodo-5-nitropyridine</strong> (250 mg, 0.88 mmol), methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (0.06 mL, 0.44 mmol) and Copper(l) iodide (25 mg, 0.13 mmol) in dimethylformamide was heated at 70 °C for 3 h under hydrogen atmosphere. Another 0.03 mL methyl 2,2-difluoro-2-(fluorosulfonyl)acetate was added and the mixture was heated at 70 °C for 16 h. The reaction mixture was cooled to room temperature, diluted with water and extracted with ethyl acetate. The organic layer was concentrated under reduced pressure to afford the crude which was purified by column chromatography to give 2-chloro-5-nitro-3-(trifluoromethyl)pyridine (41 mg, 21 percent).
21% With copper(l) iodide; hydrogen; In N,N-dimethyl-formamide; at 70℃; for 18.0h; Step 1: In a 100 mL round bottom flask, a mixture of <strong>[25391-60-0]2-chloro-3-iodo-5-nitropyridine</strong> (250 mg, 0.88 mmol), methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (0.06 mL, 0.44 mmol) and Copper(I) iodide (25 mg, 0.13 mmol) in dimethylformamide was heated at 70° C. for 3 h under hydrogen atmosphere. Another 0.03 mL methyl 2,2-difluoro-2-(fluorosulfonyl)acetate was added and the mixture was heated at 70° C. for 16 h. The reaction mixture was cooled to room temperature, diluted with water and extracted with ethyl acetate. The organic layer was concentrated under reduced pressure to afford the crude which was purified by column chromatography to give 2-chloro-5-nitro-3-(trifluoromethyl)pyridine (41 mg, 21percent).
21% With copper(l) iodide; In N,N-dimethyl-formamide; at 70℃; for 19.0h; Step 1 In a 100 mL round bottom flask, a mixture of <strong>[25391-60-0]2-chloro-3-iodo-5-nitropyridine</strong> (250 mg, 0.88 mmol), methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (0.06 mL, 0.44 mmol) and Copper(I) iodide (25 mg, 0.13 mmol) in dimethylformamide was heated at 70° C. for 3 h under hydrogen atmosphere. Another 0.03 mL methyl 2,2-difluoro-2-(fluorosulfonyl)acetate was added and the mixture was heated at 70° C. for 16 h. The reaction mixture was cooled to room temperature, diluted with water and extracted with ethyl acetate. The organic layer was concentrated under reduced pressure to afford the crude which was purified by column chromatography to give 2-chloro-5-nitro-3-(trifluoromethyl)pyridine (41 mg, 21percent).

  • 2
  • [ 680-15-9 ]
  • [ 343781-36-2 ]
  • [ 1186194-98-8 ]
YieldReaction ConditionsOperation in experiment
95% With copper(l) iodide; In N,N-dimethyl-formamide; at 100℃; for 5h;Sealed tube; Description 6 2,4-dichloro-3-trifluoromethyl-pyridine(D6)To a mixture of compound D5 (2g, 7.302 mmol) in DMF (50 ml) were added fluorosulfonyl-difluoro-acetic acid methyl ester (1.858 ml, 14.605 mmol) [C.A.S. 680- 15-9] and copper (I) iodide (2.796. g, 14.605 mmol). The reaction mixture was heated in a sealed tube at 100 0C for 5 h. After cooling, the solvent was evaporated in vacuo. The crude product was purified by column chromatography (silica gel; DCM as eluent). The desired fractions were collected and concentrated in vacuo to yield intermediate compound D6 (1.5 g, 95%).
95% With copper(l) iodide; In N,N-dimethyl-formamide; at 100℃; for 5h;Sealed tube; To a mixture of intermediate compound D12 (2g, 7.302 mmol) in DMF (50 ml) were added fluorosulfonyl-difluoro-acetic acid methyl ester (1.858 ml, 14.605 mmol)[C.A.S. 680-15-9] and copper (I) iodide (2.796. g, 14.605 mmol). The reaction mixture was heated in a sealed tube at 100 0C for 5 h. After cooling, the solvent was evaporated in vacuo. The crude product was purified by column chromatography (silica gel; DCM as eluent). The desired fractions were collected and concentrated in vacuo to yield intermediate compound D 13 ( 1.5 g, 95%).
95% With copper(l) iodide; In N,N-dimethyl-formamide; at 100℃; for 5h;Sealed tube; To a mixture of compound D24 (2g, 7.302 mmol) in DMF (50 ml) were added fiuorosulfonyl-difluoro-acetic acid methyl ester [C.A.S. 680-15-9] (1.858 ml, 14.605 mmol) and copper (I) iodine (2.796. g, 14.605 mmol). The reaction mixture was heated in a sealed tube at 100 0C for 5 h. After cooling, the solvent was evaporated in vacuo. The crude product was purified by column chromatography (silica gel; DCM as eluent). The desired fractions were collected and concentrated in vacuo to yield intermediate compound D25 (1.5 g, 95%).
95% copper(l) iodide; In N,N-dimethyl-formamide; at 100℃; for 5h;Sealed tube; Intermediate 2 (1-2)2,4-Dichloro-3 -trifluoromethyl-pyridine (1-2)To a mixture of compound 1-1 (2g, 7.30 mmol) in DMF (50 mL) were added fluorosulfonyl-difluoro-acetic acid methyl ester [C.A.S. 680-15-9] (1.86 ml,14.60 mmol) and copper (I) iodide (2.79 g, 14.60 mmol). The reaction mixture was heated in a sealed tube at 100 C for 5 h. After cooling, the solvent was evaporated in vacuo. The crude product was purified by column chromatography (silica gel, DCM). The desired fractions were collected and concentrated in vacuo to yield intermediate compound 1-2 (1.5 g, 95%).
95% copper(l) iodide; In N,N-dimethyl-formamide; at 100℃; for 5h;Sealed tube; Intermediate 8 (1-8)o-3 -trifluoromethyl-pyridine (1-2)To a mixture of compound 1-7 (2g, 7.30 mmol) in DMF (50 mL) were added fluorosulfonyl-difluoro-acetic acid methyl ester [C.A.S. 680-15-9] (1.86 ml,14.60 mmol) and copper (I) iodide (2.79 g, 14.60 mmol). The reaction mixture was heated in a sealed tube at 100 C for 5 h. After cooling, the solvent was evaporated in vacuo. The crude product was purified by column chromatography (silica gel, DCM). The desired fractions were collected and concentrated in vacuo to yield intermediate compound 1-8 (1.5 g, 95%).
95% With copper(l) iodide; In N,N-dimethyl-formamide; at 100℃; for 5h;Sealed vessel; Intermediate 2 (1-2)o-3-trifluoromethyl-pyridine (1-2)To a mixture of compound 1-1 (2g, 7.30 mmol) in DMF (50 mL) were added fluorosulfonyl-difluoro-acetic acid methyl ester [C.A.S. 680-15-9] (1.86 ml, 14.60 mmol) and copper (I) iodine (2.79 g, 14.60 mmol). The reaction mixture was heated in a sealed tube at 100 C for 5 h. After cooling, the solvent was evaporated in vacuo. The crude product was purified by column chromatography (silica gel, DCM). The desired fractions were collected and concentrated in vacuo to yield intermediate compound 1-2 (1.5 g, 95%).
95% With copper(l) iodide; In N,N-dimethyl-formamide; at 100℃; for 5h;Sealed tube; 2,4-Dichloro-3-trifluoromethyl-pyridine (I-2) To a mixture of compound I-1 (2 g, 7.30 mmol) in DMF (50 mL) were added fluorosulfonyl-difluoro-acetic acid methyl ester [C.A.S. 680-15-9] (1.86 ml, 14.60 mmol) and copper (I) iodide (2.79 g, 14.60 mmol). The reaction mixture was heated in a sealed tube at 100 C. for 5 h. After cooling, the solvent was evaporated in vacuo. The crude product was purified by column chromatography (silica gel, DCM). The desired fractions were collected and concentrated in vacuo to yield intermediate compound I-2 (1.5 g, 95%).
95% With copper(l) iodide; In N,N-dimethyl-formamide; at 100℃; for 5h;Sealed tube; 4-Dichloro-3-trifluoromethyl-pyridine (I-6) To a mixture of intermediate I-5 (2 g, 7.30 mmol) in DMF (50 mL) were added fluorosulfonyl-difluoro-acetic acid methyl ester [C.A.S. 680-15-9] (1.86 ml, 14.60 mmol) and copper (I) iodide (2.79 g, 14.60 mmol). The r.m. was heated in a sealed tube at 100 C. for 5 h. After cooling, the solvent was evaporated in vacuo. The crude product was purified by column chromatography (silica gel, DCM). The desired fractions were collected and concentrated in vacuo to yield intermediate I-6 (1.5 g, 95%).
95% With copper(l) iodide; In N,N-dimethyl-formamide; at 100℃; for 5h;Sealed tube; To a mixture of 1-1 (2 g, 7.302 mmol) in DMF (50 mL) were added fluorosulfonyl- difluoro-acetic acid methyl ester ([CAS 680-15-9], 1.858 mL, 14.605 mmol) and copper (I) iodide (2.796. g, 14.605 mmol). The reaction mixture was heated in a sealed tube at 100 C for 5 h. After cooling, the solvent was evaporated in vacuo. The crude product was purified by column chromatography (silica gel; DCM as eluent). The desired fractions were collected and concentrated in vacuo to yield 1-2 (1.5 g, 95%).
160 g With copper(l) iodide; In N,N-dimethyl-formamide; at 100℃; for 5h; To a solution of <strong>[343781-36-2]2,4-dichloro-3-iodopyridine</strong> ([CAS 34378 1-36-2], 290 g, 1058 mmol)in DMF (1.7 L) was added methyl 2,2-difluoro-2-(fluorosulfonyl)acetate ([CAS 680-15-9], 403 g, 2098 mmol) and Cul (403 g, 2.13 mol), the reaction was then heated at100Cfor5h.The reation was cooled and filtered. The filtrate was diluted with H20 and extracted with Et20 and washed with a NH3 solution. The organic layer was dried (Na2SO4), filtered and concentrated in vacuo to yield intermediate 2 (160 g), which was used without further purification.
160 g With copper(l) iodide; In N,N-dimethyl-formamide; at 100℃; for 5h; To a solution of <strong>[343781-36-2]2,4-dichloro-3-iodopyridine</strong> ([CAS 34378 1-36-2], 290 g, 1058 mmol)in DMF (1.7 L) was added methyl 2,2-difluoro-2-(fluorosulfonyl)acetate ([CAS 680-15-9], 403 g, 2098 mmol) and Cul (403 g, 2.13 mol), the reaction was then heated at i00Cfor5h.The reation was cooled and filtered. The filtrate was diluted with H20 and extracted with Et20 and washed with a NH3 solution. The organic layer was dried (Na2SO4),filtered and concentrated in vacuo to yield intermediate 2 (160 g), which was used without further purification.

  • 3
  • [ 141-32-2 ]
  • [ 680-15-9 ]
  • [ 260352-79-2 ]
  • 4
  • [ 680-15-9 ]
  • [ 401892-47-5 ]
  • [ 823221-93-8 ]
YieldReaction ConditionsOperation in experiment
64% With copper(l) iodide; In N,N-dimethyl-formamide; at 100℃; for 6h; To a stirred solution of 5-bromo-2-chloro-4-iodopyridine (40 g, 126.2 mmol, 1 eq) in DMF (400 mL) was added methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (32.1 mL, 252.5 mmol, 2 eq) followed by CuT (48.2 g, 252.5 mmol, 2 eq). The resulting mixture was heated at 100 C for 6 h. TLC analysis indicated formation of a non-polar spot. The reaction mixture was diluted with water (200 mL), filtered through a celite pad and washed with n-pentane (2 x 500 mL) and followed by cold water (3 x 1000 mL). Organic layers were separated, dried over Na2SO4 and concentrated under reduced pressure at 30 C resulted 5-bromo-2-chloro-4-(trifluoromethyl)pyridine (21 g, 64% yield) as a liquid compound. TLC: 5% EtOAc in pet ether; Rf: 0.7
55.2% With copper(l) iodide; In N,N-dimethyl-formamide; at 100℃; for 6h;Inert atmosphere; To a stirred solution of 5-bromo-2-chloro-4-iodopyridine (20.0 g, 63.09 mmol, 1.0 eq) in DMF (200 mL), methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (16.15 mL, 126.18 mmol, 2.0 eq) and Cul (24.02 g, 126.18 mmol, 2.0 eq) were added at RT under argon atmosphere and the reaction mixture was heated to 100C for 6h. TLC analysis indicated a non-polar spot. The reaction mixture was diluted with water (200 mL) and filtered off and washed with w-pentane (1L) and cold water (3L). The separated organic layer was dried over sodium sulfate and concentrated under reduced pressure at 30C. The crude compound was purified by column chromatography (Silica gel, 100-200 mesh) using 5% EtOAc in pet ether as an eluent to afford the title compound (9.0 g, 55.2%) as a liquid compound. TLC: 5% EtOAc in pet ether; Rf: 0.7
44% With copper(l) iodide; In N,N-dimethyl-formamide; at 100℃; for 6h;Inert atmosphere; To a stirred solution of 5-bromo-2-chloro-4-iodopyridine (20.0 g, 63.09 mmol) in DMF (200 mL), methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (16.15 mL, 126.18 mmol) and Cul (24.02 g, 126.18 mmol) were added at RT under argon atmosphere. The reaction mixture was heated to 100 C for 6 hours. The reaction mixture was diluted with water (200 mL) filtered off and washed with w-pentane (2 X 500 mL) and cold water (3 X 1000 mL). The separated organic layer dried over with sodium sulfate and concentrated under reduced pressure at 30 C to give the crude compound. That was purified by column chromatography (5% pet ether: EtO Ac) that resulted in the title compound (9.0g, 44%) as a liquid compound. TLC: 5% EtO Ac in pet ether. LCMS [M+H]+ = 261.0 g/mol.
  • 5
  • [ 680-15-9 ]
  • [ 80565-30-6 ]
  • 4-chloro-4'-(2,2-difluorovinyl)-1,1'-biphenyl [ No CAS ]
  • 6
  • [ 680-15-9 ]
  • [ 511533-38-3 ]
  • [ 150969-56-5 ]
YieldReaction ConditionsOperation in experiment
With N,N,N,N,N,N-hexamethylphosphoric triamide; copper(l) iodide; In N,N-dimethyl-formamide; at 85℃; for 16.0h;Inert atmosphere; To a mixture of Compound 31B (3.84 g, 14.9 mmol), copper(I) iodide (7.08 g, 37.2 mmol), and hexamethylphosphoramide (5.33 g, 29.8 mmol) in DMF (60 mL) was added methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (11.4 g, 59.6 mmol). The mixture was stirred at 85 C under nitrogen for 16 hours. The mixture was cooled down to room temperature and filtered through Celite. The filtrate was diluted with ethyl acetate (200 mL), washed with brine (100 mL x 3), dried over anhydrous sodium sulfate, filtered, and evaporated to give a crude product, which was purified with flash column chromatography on silica gel (ethyl acetate in petroleum ether, from 0% to 10% v/v) to afford Compound 31C: LC-MS (ESI) m/z: 201 [M+H]+; 1H-NMR (CDCb, 400 MHz): d (ppm) 2.77-2.80 (m, 2H), 3.22 (t, J= 6.0 Hz, 2H), 7.63 (d, J= 8.0 Hz, 1H), 7.77 (s, 1H), 7.86 (d, J= 8.0 Hz, 1H).
  • 7
  • [ 680-15-9 ]
  • [ 69605-90-9 ]
  • [ 1360594-84-8 ]
  • 8
  • [ 680-15-9 ]
  • [ 56404-21-8 ]
  • C9H8F3NO2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
71% With copper(l) iodide; N-ethyl-N,N-diisopropylamine; In N,N-dimethyl-formamide; at 80℃; for 2.0h; A mixture of l-iodo-2,4-dimethyl-3-nitrobenzene [56404-21-8] (1.50 g, 5.41 mmol), methyl 2,2-difluoro-2-(fluorosulfonyl)acetate [680-15-9] (6.24 g, 32.5 mmol), Cul (1.24 g, 6.50 mmol) and DIPEA (0.70 g, 5.41 mmol) in anhydrous DMF (13.9 mL) was stirred at 80 C for 2 h. The mixture was poured out in water and the aqueous phase was extracted with Et20. The combined organic extracts were washed with brine, dried (MgS04), filtered and concentrated under reduced pressure. The crude mixture was purified by flash column chromatography (silica, pentane/Et20, gradient from 100:0 to 90:10) to afford I- 100 (840 mg, 71%) as a yellow oil.
 

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