Benzenesulfonyl chloride → HCID 15035846, compound

HRID 1195227Notes

Reaction equation

HRID 1195227 reaction equation
[CH:1]([N:4]1[CH2:11][CH:10]2[CH2:12][CH:6]([CH2:7][NH:8][CH2:9]2)[CH2:5]1)([CH3:3])[CH3:2].[OH-].[Na+].[C:15]1([S:21](Cl)(=[O:23])=[O:22])[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.CO.C(Cl)Cl>O.C(Cl)Cl>[C:15]1([S:21]([N:8]2[CH2:9][CH:10]3[CH2:12][CH:6]([CH2:5][N:4]([CH:1]([CH3:3])[CH3:2])[CH2:11]3)[CH2:7]2)(=[O:23])=[O:22])[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Participants

7

Reactant 4

HCID 7369Benzenesulfonyl chlorideHCID 14798Sodium HydroxideHCID 150358373-Isopropyl-3,7-diazabicyclo[3.3.1]nonaneHCID 21226129Dichloromethane methanol

Product 1

HCID 15035846HCID 15035846, compoundYield 28.6%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent3×HCID 6344DichloromethaneSolvent3×

Procedure

A 50-mL, three-necked, round-bottomed flask was equipped with a magnetic stirrer, a standard condenser with a N2 inlet, an ice bath, a 10-mL addition funnel, and a glass stopper. To a stirred, ice cold (5° C.) mixture of the amine (31, 1.03 g, 6.12 mmol) and NaOH pellets (97%, 0.76 g, 18.4 mmol) in H2O (7 mL) and CH2Cl2 (5 mL) was added dropwise a solution of benzenesulfonyl chloride (2.16 g, 12.2 mmol) in CH2Cl2 (5 mL) over 30 min. Stirring of the mixture was continued for an additional 17.5 h at RT. The reaction mixture was then partioned between H2O (30 mL) and CH2Cl2 (30 mL) followed by basification (pH~12) of the aqueous phase. Extracts (CH2Cl2,3×30 mL) of the remaining water layer were combined with the initial organic layer. The solution was washed with 10% NaOH (30mL) and then saturated NaCl (30 mL); it was dried (Na2SO4, overnight), filtered, and concentrated to give an orange viscous oil. Chromatography of the oil was performed on silica gel (39 g, 1.6 cm×62 cm) using 10% CH3OH/CH2Cl2. Fractions (Rf =0.44) were saved, concentrated, and reeluted on neutral alumina (90 g, 2.5 cm×18 cm) employing ethyl acetate as eluant. Fractions (Rf =0.53) were saved and concentrated. A colored impurity persisted which was removed by again eluting over silica gel (21 g, 1.6 cm×33 cm) using 5% CH3OH/CH2Cl2 as eluant. Fractions (Rf =0.34) were combined and concentrated (rotary evaporator then vacuum pump, overnight, RT/0.2 mm Hg) to give 0.54 g (28.6%) of white solid (36); mp 85.5°-86.5° C. IR (KBr) cm-1 3060 (Ar C--H), 2960, 2910, 2890, 2865, 2820 (C--H), 1585 (C=C), 1340, 1170 (S=O), 760, 720 (C--H out of plane, mono); 1H NMR (DMSO-d6) δ0.88 (d, 6H, CH3, J=6.5 Hz), 1.40 [bs, 2H, H(9)], 1.94 [bs, 2H, H(1,5)], 2.35 [bd, 2H, H(6,8)ax, J=10.3 Hz], 2.53 [heptet, 1H, CH(CH3)2, J=6.5 Hz], 2.69 [bd, 2H, H(6,8)eq, J=10.3 Hz], 2.89 [dd, 2H, H(2,4)ax, J=11.2 Hz, J'=4.5 Hz], 3.36 [d, 2H, H(2,4)eq, J=10.9 Hz], 7.58-7.75 (m, 5H, Ar--H); 13C NMR (DMSO-d6) ppm 17.57 (CH3), 27.39 [C(1,5)], 28.95 [C(9)], 48.88 [C(2,4)], 52.66[C(6,8)], 53.42 [CH(CH3)2 ], 126.90, 129.01, 132.36, 136.79 (Ar--C). Anal. Calcd. for C16H24N2O2S: C, 62.31; H, 7.85. Found: C, 62.48; H, 7.69.

Workup

  1. customA 50-mL, three-necked, round-bottomed flask was equipped with a magnetic stirrer, a standard condenser with a N2 inlet, an ice bath, a 10-mL addition funnel
  2. washThe solution was washed with 10% NaOH (30mL)
  3. dry with materialit was dried (Na2SO4, overnight)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto give an orange viscous oil
  7. concentrationconcentrated
  8. concentrationconcentrated
  9. customwas removed
  10. washby again eluting over silica gel (21 g, 1.6 cm×33 cm)
  11. concentrationconcentrated (
  12. customrotary evaporator

Sources & evidence

ORD record
ord-1cd0df99260847b88d56a6f6b9f7af88
Source dataset
uspto-grants-1992_05
Patent number
US05110933

Reaction notes

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