Dimethylformamide → HCID 86623507, compound

HRID 2075283Notes

Reaction equation

HRID 2075283 reaction equation
[OH:1][N:2]1[C:6](=[O:7])[CH2:5][CH2:4][C:3]1=[O:8].[Cl:9][C:10]1[CH:15]=[CH:14][C:13](CCl)=[CH:12][N:11]=1.[CH3:18]N(C=O)C.C([O-])([O-])=O.[K+].[K+]>O>[Cl:9][C:10]1[CH:15]=[CH:14][C:13]([CH:4]2[CH2:5][C:6](=[O:7])[N:2]([O:1][CH3:18])[C:3]2=[O:8])=[CH:12][N:11]=1

Participants

6

Reactant 4

HCID 6228Dimethylformamide2×HCID 11430Potassium CarbonateHCID 80170N-HydroxysuccinimideHCID 1554792-Chloro-5-(chloromethyl)pyridine

Product 1

HCID 86623507HCID 86623507, compoundYield 49%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
15.5 °C

Procedure

To a 5 L-three neck flask equipped with a mechanic stirrer, heating mantle with temperature controller and a gas outlet, were charged N-hydroxysuccinimide (426 g, 3.7 mol), 2-chloro-5-chloromethylpyridine (500 g, 3.1 mol) and anhydrous DMF (1 L). The mixture was stirred for 5 min when inner temperature dropped to 8.5° C. Anhydrous K2CO3 (640 g, 4.6 mol) was charged in one portion followed by anhydrous DMF (0.5 L). It was stirred for 5 min when inner temperature raised to 15.5° C. The mixture was heated to 70° C. (preset) within 30 min but the temperature continued to rise to 89° C. over 1 h of reaction period, during which a lot of gas was evolved and the reaction was finished as judged by MS and TLC, or simply the termination of gas-evolving. It was cooled down to room temperature, poured into water (6 L) with mechanic stirring. The insoluble was collected by filtration and washed with water (1.5 L), air-dried for 60 h to give the desired product as an off-white powder (364 g, 49%). ESIMS m/e (M+H)+: 241. 1H NMR (500 MHz, CDCl3): 8.44 (s, 1H), 7.95 (d, 1H, 3J=8.5 Hz), 7.41 (d, 1H, 3J=8.0 Hz), 5.14 (s, 2H), 2.73 (s, 4H) ppm. 13C NMR (125 MHz, CDCl3): δ 170.8, 152.6, 150.2, 140.2, 128.2, 124.4, 74.9, 25.4.

Workup

  1. customTo a 5 L-three neck flask equipped with a mechanic stirrer
  2. temperatureheating mantle with temperature controller and a gas outlet
  3. additiondropped to 8.5° C
  4. stirringIt was stirred for 5 min when inner temperature
  5. temperatureThe mixture was heated to 70° C. (preset) within 30 min
  6. customto rise to 89° C. over 1 h of reaction period, during which a lot of gas
  7. temperatureIt was cooled down to room temperature
  8. filtrationThe insoluble was collected by filtration
  9. washwashed with water (1.5 L)
  10. customair-dried for 60 h

Sources & evidence

ORD record
ord-2b920e445b2940f6b855b5691fb92302
Source dataset
uspto-grants-2011_04
Patent number
US07919627B2

Reaction notes

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