Dimethyl Sulfoxide → HCID 25019977, compound

HRID 1259459Notes

Reaction equation

HRID 1259459 reaction equation
CC1C=CC(S(O[CH2:12][CH:13]2[O:18][C:17]3[CH:19]=[C:20]([N+:23]([O-:25])=[O:24])[CH:21]=[CH:22][C:16]=3[O:15][CH2:14]2)(=O)=O)=CC=1.CS(C)=O.[CH2:30]([NH2:37])[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1>O>[CH2:30]([NH:37][CH2:12][C@@H:13]1[O:18][C:17]2[CH:19]=[C:20]([N+:23]([O-:25])=[O:24])[CH:21]=[CH:22][C:16]=2[O:15][CH2:14]1)[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1

Participants

5

Reactant 3

HCID 679Dimethyl SulfoxideHCID 7504BenzylamineHCID 22238110(7-Nitro-2,3-dihydrobenzo[b][1,4]dioxin-2-yl)methyl 4-methylbenzenesulfonate

Product 1

HCID 25019977HCID 25019977, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
90 °C

Procedure

A 3 L three necked flask equipped with a heating mantle, thermocouple and mechanical stirrer is charged with [7-nitro-2,3-dihydro-1,4-benzodioxin-2-yl]methyl 4-methylbenzenesulfonate (356.8 g, 0.977 mol), DMSO (1 L) and benzylamine (261.7 g, 2.44 mol). The slurry is heated to maintain an internal temperature of 90° C. Heating is continued for 18 h, and then the solution is allowed to cool to 30° C. over 2 h. Water (400 mL) is added over 15 min. then seed crystals (˜100 mg) are added resulting in rapid formation of a precipitate. The slurry is stirred for 30 min prior to additional water (2 L) being added over 1.5 h. The slurry is stirred for 4 h, the solids are collected by vacuum filtration, washed with water (2 L) and suction dried under nitrogen giving the title compound (302.87 g, 103%) as a yellow powder (94% ee). Yield is high due to trapped water, m.p. 98° C. (dried sample). LCMS (Basic Method): 2.05 min, 301 (M+H)+. 1H NMR (300 MHz, DMSO-d6) δ 7.77-7.70 (m, 1H), 7.47-7.18 (m, 6H), 7.10-7.06 (m, 1H), 4.47 (dd, J=2.5, 11.5 Hz, 1H), 4.37-4.29 (m, 1H), 4.15 (dd, J=7.1, 11.5 Hz, 1H), 3.73 (s, 2H), 2.82-2.70 (m, 2H), 2.43 (br s, 1H).

Workup

  1. temperatureThe slurry is heated
  2. temperatureHeating
  3. temperatureto cool to 30° C. over 2 h
  4. customresulting in rapid formation of a precipitate
  5. stirringThe slurry is stirred for 4 h
  6. filtrationthe solids are collected by vacuum filtration
  7. washwashed with water (2 L) and suction
  8. dry with materialdried under nitrogen giving the title compound (302.87 g, 103%) as a yellow powder (94% ee)
  9. customYield
  10. dry with materialis high due to trapped water, m.p. 98° C. (dried sample)
  11. custom2.05 min, 301 (M+H)+

Sources & evidence

ORD record
ord-058ef1686c3f40b292cc319b9b23b193
Source dataset
uspto-grants-2013_06
Patent number
US08466296B2

Reaction notes

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