Iodine → Methanesulfonic acid--1-[(4-methylphenyl)methyl]hydrazine-1-carboxamide (1/1)

HRID 968833Notes

Reaction equation

HRID 968833 reaction equation
[NH2:1][C:2]([N:4]([CH2:13][C:14]1[CH:19]=[CH:18][C:17]([CH3:20])=[CH:16][CH:15]=1)[NH:5]C(OC(C)(C)C)=O)=[O:3].ClCCl.[CH3:24][S:25]([OH:28])(=[O:27])=[O:26].II>CCCCCCC.C(OCC)(=O)C.O>[CH3:24][S:25]([OH:28])(=[O:27])=[O:26].[CH3:20][C:17]1[CH:18]=[CH:19][C:14]([CH2:13][N:4]([C:2]([NH2:1])=[O:3])[NH2:5])=[CH:15][CH:16]=1

Participants

8

Reactant 4

HCID 807IodineHCID 6344DichloromethaneHCID 6395Methanesulfonic AcidHCID 23584127HCID 23584127, compound

Product 1

HCID 57349926Methanesulfonic acid--1-[(4-methylphenyl)methyl]hydrazine-1-carboxamide (1/1)Yield 98.6%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 8900HeptaneSolvent

Conditions

Temperature
32.5 °C

Procedure

A 22-L 4-neck flask was equipped with an overhead stirring apparatus, warming/cooling bath, thermometer probe, condenser, and 500-mL addition funnel. The flask was charged with 2-(Aminocarbonyl)-2-(4-methylphenylmethyl)-hydrazine carboxylic acid, 1,1-dimethylethyl ester (1100 g, 3.94 moles) and dichloromethane (12 L). The mixture was warmed to 30-35° C. to completely dissolve all solids, then cooled to 25-30° C. and methanesulfonic acid (MsOH) (398 g, 4.14 moles) was added over 30 min. The water bath was replaced with a heating mantle and the reaction solution was heated at reflux for 12-20 hours, and, monitored by TLC analysis (Ethyl Acetate 100%; I2, Rf(sm)=0.3, Rf(prod)=0.1) When complete, the reaction mixture was diluted with heptane (4000 mL), cooled to 10-20° C., and stirred for 30 min. After filtration, the cake was washed with heptane (2×1000 mL) and dried in vacuo at 35-45° C., to afford the title compound as a white solid (1070 g, 98.6%). 1H NMR (DMSO-d6, 300 MHz): δ 1.35 (s, 9 H), 2.26 (s, 1 H), 4.45 (br s, 2 H), 6.06 (s, 2 H), 7.10 (s, 4 H), 8.88 (br s, 1 H); Anal. Calcd. for C10H17N3O4 S,: C, 43.62; H, 6.22; N, 15.26; S, 11.64. Found: C, 43.33; H, 6.21; N, 14.97.

Workup

  1. customA 22-L 4-neck flask was equipped with an overhead
  2. temperaturewarming/cooling bath
  3. additionthermometer probe, condenser, and 500-mL addition funnel
  4. dissolutionto completely dissolve all solids
  5. temperaturecooled to 25-30° C.
  6. temperaturethe reaction solution was heated
  7. temperatureat reflux for 12-20 hours
  8. temperaturecooled to 10-20° C.
  9. stirringstirred for 30 min
  10. filtrationAfter filtration
  11. washthe cake was washed with heptane (2×1000 mL)
  12. customdried in vacuo at 35-45° C.

Sources & evidence

ORD record
ord-f61571d1c59c4fb4a7b967df64e37f12
Source dataset
uspto-grants-2007_12
Patent number
US07304062B2

Reaction notes

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