Hydrogen Peroxide → N-(2-methylsulfinyl-1,1-dimethyl-ethyl)-N'-(2-methyl-4-(1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl)phenyl)phthalamide

HRID 2358871Notes

Reaction equation

HRID 2358871 reaction equation
[OH-].[Na+].C(=O)([O-])O.[Na+].[CH3:8][C:9]([NH2:14])([CH3:13])[CH2:10][S:11][CH3:12].[C:15](Cl)(=[O:25])[C:16]1[C:17](=[CH:21][CH:22]=[CH:23][CH:24]=1)[C:18](Cl)=[O:19].[Cl-].[Na+].C1(=O)NC(=[O:35])C2=CC=CC1=C2.OO.[CH3:42][C:43]1[CH:49]=[C:48]([C:50]([F:59])([C:55]([F:58])([F:57])[F:56])[C:51]([F:54])([F:53])[F:52])[CH:47]=[CH:46][C:44]=1[NH2:45].S([O-])([O-])=O.[Na+].[Na+]>O.O.C1(C)C=CC(S(O)(=O)=O)=CC=1.ClC1C=CC=CC=1>[CH3:8][C:9]([NH:14][C:15]([C:16]1[C:17]([C:18]([NH:45][C:44]2[CH:46]=[CH:47][C:48]([C:50]([F:59])([C:51]([F:53])([F:54])[F:52])[C:55]([F:56])([F:57])[F:58])=[CH:49][C:43]=2[CH3:42])=[O:19])=[CH:21][CH:22]=[CH:23][CH:24]=1)=[O:25])([CH3:13])[CH2:10][S:11]([CH3:12])=[O:35]

Participants

13

Reactant 9

HCID 784Hydrogen PeroxideHCID 5234Sodium ChlorideHCID 6955Phthaloyl chlorideHCID 14798Sodium HydroxideHCID 24437Sodium SulfiteHCID 516892Sodium Bicarbonate2×HCID 99255434-(1,1,1,2,3,3,3-Heptafluoropropan-2-yl)-2-methylanilineHCID 120973802-Propanamine, 2-methyl-1-(methylthio)-HCID 18926764Isophthalimide

Product 1

HCID 22066255N-(2-methylsulfinyl-1,1-dimethyl-ethyl)-N'-(2-methyl-4-(1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl)phenyl)phthalamideYield 85%

Reagents, catalysts & solvents 3

HCID 521998p-Toluenesulfonic acid monohydrateCatalystHCID 962WaterSolventHCID 7964ChlorobenzeneSolvent2×

Conditions

Temperature
40 °C

Procedure

Sodium hydroxide (0.83 g) and sodium hydrogencarbonate (1.66 g) were dissolved in water (12 mL), followed by adding thereto 2-methyl-1-methylthio-2-propanamine (2.62 g) and chlorobenzene (12 mL), and to the resulting mixture was added dropwise phthaloyl dichloride (4 g) at 40° C. or lower. After completion of the dropwise addition, the resulting mixture was stirred at 40° C. for 30 minutes and sodium chloride (1.73 g) was added thereto. Thereafter, the organic layer was separated to prepare a solution of N-[1,1-dimethyl-2-(methylthio)ethyl]isophthalimide in chlorobenzene. The previously prepared isophthalimide solution and 15% hydrogen peroxide (4.9 g) were alternately and slowly dropped into a mixture of 2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]aniline (5.15 g), p-toluenesulfonic acid monohydrate (0.09 g) and chlorobenzene (3 mL) at 50° C. and then stirred at 60° C. for 3 hours. An aqueous sodium sulfite solution was added dropwise to the thus obtained reaction mixture at the same temperature to decompose the excess oxidizing agent. After neutralization with an aqueous sodium hydrogencarbonate solution, the resulting mixture was slowly cooled to 20° C. The crystals precipitated were filtered, washed with water and then dried to obtain 9.06 g (yield 85%) of the title compound.

Workup

  1. additionby adding
  2. additionAfter completion of the dropwise addition
  3. customThereafter, the organic layer was separated
  4. customto prepare a solution of N-[1,1-dimethyl-2-(methylthio)ethyl]isophthalimide in chlorobenzene
  5. stirringstirred at 60° C. for 3 hours
  6. customThe crystals precipitated
  7. filtrationwere filtered
  8. washwashed with water
  9. customdried

Sources & evidence

ORD record
ord-4b910b3dbd0d4313bcc4f5c356eb621c
Source dataset
uspto-grants-2010_07
Patent number
US07763750B2

Reaction notes

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