2-Aminothiophenol → 2,2'-(Ethylenedithio)dianiline

HRID 2410210Notes

Reaction equation

HRID 2410210 reaction equation
[OH-].[K+].[NH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[SH:10].[K].I[CH2:13][CH2:14]I>C(O)(C)C>[CH2:5]([S:10][C:14]1[CH:13]=[CH:7][CH:8]=[CH:9][C:4]=1[NH2:3])[CH2:6][S:10][C:5]1[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=1[NH2:3]

Participants

6

Reactant 4

HCID 87132-AminothiophenolHCID 122241,2-DiiodoethaneHCID 14797Potassium Hydroxide2×HCID 5462222Potassium

Product 1

HCID 923432,2'-(Ethylenedithio)dianilineYield 58.6%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent2×

Procedure

A 4-necked, 1-L flask was fitted with a reflux condenser, nitrogen line, mechanical stirrer (PTFE bearing and paddle), thermocouple, pressure-equilibrated dropping funnel, and a mantle. The flask was charged with 300 mL of isopropyl alcohol followed by 42.0 g of potassium hydroxide. The mixture was stirred under nitrogen at ca. 300 rpm until the KOH was partially dissolved. 88.86 g of 2-aminothiophenol was then added over 1.25 r. This was accompanied by an exotherm and the formation of a suspension of the potassium salt. 99.71 g of 1,2-diiodoethane suspended in 200 mL isopropanol at 50° C. was then added over ca. 0.25 hr. The resultant suspension was heated at 80° C. for 8.9 h. The reaction mixture was filtered hot through Whatman GF/A paper. The filter cake was washed with 100 mL isopropanol. The weight of the filter cake was 95.25 g. The filtrate crystallized while cooling overnight to room temperature. The crystals were isolated by suction filtration through Whatman #1 paper. The yellow crystals were dried on a rotary evaporator (1 torr final vacuum, 90° C. water bath) to afford 57.32 g (58.5%) of a yellow solid.

Workup

  1. dissolutionwas partially dissolved
  2. additionwas then added over ca. 0.25 hr
  3. filtrationThe reaction mixture was filtered hot through Whatman GF/A paper
  4. washThe filter cake was washed with 100 mL isopropanol
  5. customThe filtrate crystallized
  6. temperaturewhile cooling overnight to room temperature
  7. customThe crystals were isolated by suction filtration through Whatman #1 paper
  8. dry with materialThe yellow crystals were dried on a rotary evaporator (1 torr final vacuum, 90° C. water bath)

Sources & evidence

ORD record
ord-8353b6f6d72347e29b1ac8bbb23617f6
Source dataset
uspto-grants-2014_08
Patent number
US08816044B2

Reaction notes

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