Thiophenol → Bis(phenylsulfanyl)maleimide

HRID 929381Notes

Reaction equation

HRID 929381 reaction equation
Br[C:2]1[C:7](=[O:8])[NH:6][C:4](=[O:5])[C:3]=1Br.C(=O)([O-])O.[Na+].[C:15]1([SH:21])[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>CO>[C:15]1([S:21][C:3]2[C:4](=[O:5])[NH:6][C:7](=[O:8])[C:2]=2[S:21][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Participants

5

Reactant 3

HCID 7969ThiophenolHCID 14279DibromomaleimideHCID 516892Sodium Bicarbonate

Product 1

HCID 12553299Bis(phenylsulfanyl)maleimideYield 77.6%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

To dibromomaleimide (80.0 mg, 0.3 mmol) and sodium hydrogencarbonate (130.2 mg, 1.6 mmol) in methanol (6 ml) was slowly added benzenethiol (66.6 μl, 0.7 mmol) in methanol (1 ml). The reaction was stirred for 15 min at RT. The solvent was removed in vacuo and the residual material was purified by flash chromatography on silica gel (petroleum ether: ethyl acetate, gradient elution from 9:1 to 7:3) to afford the desired product as bright yellow crystals (73 mg, 75%). λmax (50 mM sodium phosphate, pH 6.2, 40% MeCN, 2.5% DMF)/412 nm (ε/dm3 mol−1 cm−1 2245); 1H NMR (500 MHz, MeOD): δ=7.27-7.22 (m, 6H, Ar—H), 7.16-7.14 (m, 4H, Ar—H); 13C NMR (125 MHz, MeOD): δ=169.3 (C), 137.6 (C), 135.4 (C), 132.4 (CH), 130.1 (CH), 129.1 (CH); IR (solid, cm−1): 3285 (m), 3059 (w), 2924 (w), 1774 (m), 1715 (s); MS (CI) m/z, (%): 314 (M+H, 100), 206 (13), 111 (12); Mass calc. for C16H11O2NS2[H]: 314.0231. Found: 314.0309; m.p. 102-104° C. (Literature: 123-126° C.).

Workup

  1. customThe solvent was removed in vacuo
  2. customthe residual material was purified by flash chromatography on silica gel (petroleum ether: ethyl acetate, gradient elution from 9:1 to 7:3)

Sources & evidence

ORD record
ord-0e9392f3fc3440559b1fee0129cf508d
Source dataset
uspto-grants-2016_03
Patent number
US09295729B2

Reaction notes

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