Chlorosulfonyl isocyanate → HCID 67063478, compound

HRID 601126Notes

Reaction equation

HRID 601126 reaction equation
[CH:1]1([C:7]2[CH:13]=[CH:12][C:10]([NH2:11])=[CH:9][CH:8]=2)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.Cl[S:15]([N:18]=C=O)(=[O:17])=[O:16].[Cl-].[Cl-].[Cl-].[Al+3]>[N+](CC)([O-])=O>[NH2:11][C:10]1[CH:9]=[CH:8][C:7]([CH:1]2[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6]2)=[CH:13][C:12]=1[S:15]([NH2:18])(=[O:17])=[O:16]

Participants

5

Reactant 3

HCID 70918Chlorosulfonyl isocyanateHCID 807644-CyclohexylbenzenamineHCID 6451240Aluminum(III) Chloride

Product 1

HCID 67063478HCID 67063478, compoundYield 31%

Reagents, catalysts & solvents 1

HCID 6587NitroethaneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 4-cyclohexylaniline (0.877 g, 5.0 mmol, 1.0 eq) in nitroethane (5 mL) was cooled to −40° C., treated dropwise with chlorosulfonyl isocyanate (0.87 g, (0.523 mL, 6.15 mmol, 1.23 eq), warmed to 0° C., treated with aluminum trichloride (0.85 g, 6.35 mmol, 1.27 eq), heated in a 110° C. oil bath for 30 minutes, cooled to ambient temperature, and poured into 200 mL of ice water. The mixture was filtered and the filter cake was rinsed with cold water, dissolved in 50% H2SO4 (25 mL), heated to reflux for 4 hours, cooled to ambient temperature, poured into 200 mL of ice water, and carefully neutralized to pH 7 with 40% NaOH. The reaction mixture was extracted with ethyl acetate (3×100 mL) and the combined extracts were washed with brine, dried (MgSO4), filtered, and concentrated to give 0.40 g of the desired product (31% yield). MS (ESI+) m/z 255.0 (M+H)+, 272.1 (M+H2O)+, 277.0 (M+Na)+; 1H NMR (300 MHz, DMSO-d6) δ 1.32 (m 4H), 1.71 (m, 6H), 2.36 (m, 1H), 5.64 (s, 2H), 6.72 (d, J=8.09 Hz, 1H), 7.11 (dd, J=8.46, 2.21 Hz, 1H), 7.16 (s, 2H), 7.38 (d, J=2.21 Hz, 1H).

Workup

  1. temperatureheated in a 110° C. oil bath for 30 minutes
  2. temperaturecooled to ambient temperature
  3. filtrationThe mixture was filtered
  4. washthe filter cake was rinsed with cold water
  5. dissolutiondissolved in 50% H2SO4 (25 mL)
  6. temperatureheated
  7. temperatureto reflux for 4 hours
  8. temperaturecooled to ambient temperature
  9. additionpoured into 200 mL of ice water
  10. extractionThe reaction mixture was extracted with ethyl acetate (3×100 mL)
  11. washthe combined extracts were washed with brine
  12. dry with materialdried (MgSO4)
  13. filtrationfiltered
  14. concentrationconcentrated

Sources & evidence

ORD record
ord-427e5e3877b54592880d7bafc86b4c62
Source dataset
uspto-grants-2011_03
Patent number
US07902203B2

Reaction notes

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