Water → 1246203-64-4

HRID 1619865Notes

Reaction equation

HRID 1619865 reaction equation
[N:1]1([C:7]([O:9][CH2:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[O:8])[CH2:6][CH2:5][NH:4][CH2:3][CH2:2]1.CCN(C(C)C)C(C)C.Cl[CH2:27][CH2:28][S:29](Cl)(=[O:31])=[O:30].O>C(Cl)Cl>[CH:28]([S:29]([N:4]1[CH2:5][CH2:6][N:1]([C:7]([O:9][CH2:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[O:8])[CH2:2][CH2:3]1)(=[O:31])=[O:30])=[CH2:27]

Participants

6

Reactant 4

HCID 962WaterHCID 15385Ethanesulfonylchloride, 2-chloro-HCID 81531DiisopropylethylamineHCID 643495Benzyl piperazine-1-carboxylate

Product 1

HCID 666980981246203-64-4Yield 43%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-15 °C

Procedure

A mixture of 11 g (50 mmol) of benzyl 1-piperazinecarboxylate and 16.1 g (125 mmol) of DIPEA in 200 mL CH2Cl2 was cooled to −15° C. and 6.3 mL (9.8 g, 60 mmol) of 2-chloroethanesulfonyl chloride was added slowly over 15 min. The mixture was allowed to warm to 0° C. over 30 min and water was then added. The organic layer was separated and washed successively with dil. HCl and aq. NaHCO3. After drying, the solvent was removed and the residue was chromatographed on silica, eluting with CH2Cl2/EtOAc 95:5, to give an oil, which was recrystallized from CH2Cl2/hexanes to give 6.64 g (43% yield) of benzyl 4-(vinylsulfonyl)-1-piperazinecarboxylate: mp (CH2Cl2/hexanes) 85-87° C.; 1H NMR (CDCl3) δ 7.39-7.30 (m, 5H), 6.40 (dd, J=16.6, 9.8 Hz, 1H), 6.25 (d, J=16.6 Hz, 1H), 6.06 (d, J=9.8 Hz, 1H), 5.14 (s, 2H), 3.61 (m, 4H), 3.14 (m, 4H); Anal. Calcd. for C14H18N2O4S: C, 54.2; H, 5.85; N, 9.0. Found: C, 54.1; H, 5.7; N, 9.1%.

Workup

  1. temperatureto warm to 0° C. over 30 min
  2. customThe organic layer was separated
  3. washwashed successively with dil. HCl and aq. NaHCO3
  4. customAfter drying
  5. customthe solvent was removed
  6. customthe residue was chromatographed on silica
  7. washeluting with CH2Cl2/EtOAc 95:5
  8. customto give an oil, which
  9. customwas recrystallized from CH2Cl2/hexanes

Sources & evidence

ORD record
ord-478f64e18c074fea9ec2c2c7a969ea14
Source dataset
uspto-grants-2014_07
Patent number
US08772287B2

Reaction notes

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