Chlorosulfonyl isocyanate → HCID 118294448, compound

HRID 1048841Notes

Reaction equation

HRID 1048841 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:13]2[CH:18]=[CH:17][C:16]([OH:19])=[CH:15][CH:14]=2)[CH:6]=[CH:7][C:8]=1[CH:9]([CH3:12])[C:10]#[CH:11].ClS([N:24]=[C:25]=[O:26])(=O)=O>C(Cl)Cl>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:13]2[CH:14]=[CH:15][C:16]([O:19][C:25](=[O:26])[NH2:24])=[CH:17][CH:18]=2)[CH:6]=[CH:7][C:8]=1[CH:9]([CH3:12])[C:10]#[CH:11]

Participants

4

Reactant 2

HCID 70918Chlorosulfonyl isocyanateHCID 118294438HCID 118294438, compound

Product 1

HCID 118294448HCID 118294448, compoundYield 68%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a 25 mL flame dried flask with stir bar cooled to room temperature was added alkyne 20 (0.115 g, 0.46 mmol) dissolved in anhydrous CH2Cl2. The reactant was cooled to 0° C. and chlorosulfonyl isocyanate (0.08 mL, 0.92 mmol) was added dropwise. After 15 min, the reaction mixture was brought to room temperature and followed by TLC. The reaction was quenched with water and extracted with ether. The organic extracts were washed with brine, dried over MgSO4, and filtered. The filtrate was concentrated and purified by flash column chromatography (SiO2, 7 g, 25% EtOAc/hexanes) to give the terminal acetylene 23 as a white solid (0.092 g, 68% yield): TLC Rf=0.1 (25% EtOAc/hexanes); mp 113.6-115.3° C.; 1H NMR (500 MHz, CDCl3) δ 7.61 (d, J=7.8 Hz, 1H), 7.56 (d, J=8.5 Hz, 2H), 7.19 (d, J=8.5 Hz, 2H), 7.15 (dd, J=7.8, 1.4 Hz, 1H), 7.01 (d, J=1.7 Hz, 1H), 4.21 (qd, J=7.0, 2.3 Hz, 1H), 3.88 (s, 3H), 2.23 (d, J=2.4 Hz, 1H), 1.47 (d, J=7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 189.2, 156.4, 155.6, 150.3, 140.6, 138.9, 133.1, 130.3, 128.3, 128.2, 122.1, 119.7, 109.6, 87.7, 69.6, 60.6, 55.7, 25.3, 22.8, 21.2, 14.4; IR (neat cm−1) 3423, 3308, 3268, 3199, 2969, 2341, 2105, 1698, 1606, 1494, 1378, 1213, 586; HRMS (DART, M++H) m/z 296.1300 (calculated for C18H18NO3, 296.1287).

Workup

  1. temperatureTo a 25 mL flame
  2. customdried flask
  3. temperatureThe reactant was cooled to 0° C.
  4. customwas brought to room temperature
  5. customThe reaction was quenched with water
  6. extractionextracted with ether
  7. washThe organic extracts were washed with brine
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. concentrationThe filtrate was concentrated
  11. custompurified by flash column chromatography (SiO2, 7 g, 25% EtOAc/hexanes)

Sources & evidence

ORD record
ord-c715c588808946d88ed153a1c64c9cb5
Source dataset
uspto-grants-2016_07
Patent number
US09382213B2

Reaction notes

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