Aniline → 2-(methylthio)-N-phenylaniline

HRID 403138Notes

Reaction equation

HRID 403138 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[S:8][CH3:9].COC1C=CC=C(OC)C=1C1C=CC=CC=1P(C1CCCCC1)C1CCCCC1.CC(C)([O-])C.[Na+].[NH2:45][C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(C)C=CC=CC=1>[CH3:9][S:8][C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[NH:45][C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1

Participants

7

Reactant 4

HCID 6115AnilineHCID 881662-BromothioanisoleHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 23676156Sodium t-butoxide

Product 1

HCID 140448122-(methylthio)-N-phenylaniline

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

(2-bromophenyl)(methyl)sulfane (25 g, 123 mmol), Pd2dba3 (6.75 g, 7.38 mmol), S-Phos (6.06 g,14.77 mmol) and sodium tert-butoxide (17.74 g, 185 mmol) were placed in a dry 3 neck flask under N2. The reaction mixture was vacuum evacuated and back filled with N2 three times. Aniline (22.93 g, 246 mmol) and 500 mL toluene were added to the reaction mixture. The reaction mixture was refluxed for 18 hours. The crude reaction mixture was run through a silica gel plug and eluted with toluene. The toluene portion was concentrated down and subjected to a silica gel column by using 3-5% DCM in hexanes to yield desired product. (24 g, 111 mmol, 91%)

Workup

  1. customa dry 3 neck flask under N2
  2. customevacuated
  3. additionback filled with N2 three times
  4. temperatureThe reaction mixture was refluxed for 18 hours
  5. customThe crude reaction mixture
  6. washeluted with toluene
  7. concentrationThe toluene portion was concentrated down

Sources & evidence

ORD record
ord-c95a082f2f3542ee99296d479c847c81
Source dataset
uspto-grants-2014_06
Patent number
US08748011B2

Reaction notes

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