Benzenesulfonyl chloride → HCID 15035846, compound

HRID 1091197Notes

Reaction equation

HRID 1091197 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 962WaterSolventHCID 6344DichloromethaneSolvent2×

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 partitioned 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 (30 mL) 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, 6 H, CH3, J=6.5 Hz), 1.40 [bs, 2 H, H(9)], 1.94 [bs, 2 H, H(1,5)], 2.35 [bd, 2 H, H(6,8)ax, J=10.3 Hz], 2.53 [heptet, 1 H, CH(CH3)2, J=6.5 Hz], 2.69 [bd, 2 H, H(6,8)eq, J=10.3 Hz], 2.89 [dd, 2 H, H(2,4)ax, J=11.2 Hz, J'=4.5 Hz], 3.36 [d, 2 H, H(2,4)eq, J=10.9 Hz], 7.58-7.75 (m, 5 H, Ar--H); 13C NMR (DMSO-d 6) 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. customThe reaction mixture was then partitioned between H2O (30 mL) and CH2Cl2 (30 mL)
  3. washThe solution was washed with 10% NaOH (30 mL)
  4. dry with materialit was dried (Na2SO4, overnight)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto give an orange viscous oil
  8. concentrationconcentrated
  9. concentrationconcentrated
  10. customwas removed
  11. washby again eluting over silica gel (21 g, 1.6 cm×33 cm)
  12. concentrationconcentrated (
  13. customrotary evaporator

Sources & evidence

ORD record
ord-df142f5f38ef40208e8243b740ea5940
Source dataset
uspto-grants-1992_01
Patent number
US05084572

Reaction notes

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