Pyridine → HCID 86629138, compound

HRID 556728Notes

Reaction equation

HRID 556728 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:16]=[CH:17][C:18]=1[O:19][CH3:20])[CH2:6][CH2:7][O:8][C@H:9]1[CH2:14][CH2:13][CH2:12][CH2:11][C@H:10]1[OH:15].N1C=CC=CC=1.[N+:27]([C:30]1[CH:35]=[CH:34][C:33]([S:36](Cl)(=[O:38])=[O:37])=[CH:32][CH:31]=1)([O-:29])=[O:28]>ClCCl>[N+:27]([C:30]1[CH:31]=[CH:32][C:33]([S:36]([O:15][C@@H:10]2[CH2:11][CH2:12][CH2:13][CH2:14][C@@H:9]2[O:8][CH2:7][CH2:6][C:5]2[CH:16]=[CH:17][C:18]([O:19][CH3:20])=[C:3]([O:2][CH3:1])[CH:4]=2)(=[O:38])=[O:37])=[CH:34][CH:35]=1)([O-:29])=[O:28]

Participants

5

Reactant 3

HCID 1049PyridineHCID 74044-Nitrobenzenesulfonyl chlorideHCID 58637349HCID 58637349, compound

Product 1

HCID 86629138HCID 86629138, compoundYield 72.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

A 10-mL round bottom flask under nitrogen atmosphere was charged with cis-2-(3,4-dimethoxyphenethoxy)cyclohexan-1-ol (13) (80 mg, 0.28 mmol), anhydrous dichloromethane (3 mL), and anhydrous pyridine (70 μL, 0.86 mmol). After the reaction mixture was cooled to 0° C., a solution of 4-nitro-benzenesulfonyl chloride (95 mg, 0.43 mmol) in anhydrous dichloromethane (1.5 mL) was added dropwise. The reaction was stirred at 0° C. for 30 minutes, and then at room temperature until total consumption of all starting material 13 (20 h), as revealed by TLC (1:1, v/v EtOAc:hexane). The reaction mixture was diluted with dichloromethane (10 mL) and aqueous H2SO4 (5%, 10 mL). After the aqueous layer was extracted with CH2Cl2 (2×10 mL), the organic layers were combined, washed successively with diluted aqueous H2SO4 (5%, 10 mL) and brine (10 mL), dried (anhydrous MgSO4), and concentrated in vacuo to give a yellow oil. Purification of this crude material by elution through a silica gel plug using a mixture of ethyl acetate-hexanes (1:2, v/v) afforded 14 (95 mg, 72%). Rf 0.71 (EtOAc-hexanes, 1:1, v/v); 1H-NMR (400 MHz, CDCl3) δ 1.21-1.69 (m, 8H), 2.01-2.11 (m, 1H), 2.63 (t, 2H, J 6.9 Hz), 3.36-3.38 (m, 1H), 3.43-3.57 (m, 2H), 3.83 (s, 6H, OCH3), 4.84-4.86 (m, 1H), 6.63-6.69 (m, 2H), 6.75 (d, 1H, J 8.1 Hz), 8.01-8.05 (m, 2H), 8.24-8.28 (m, 2H); 13C-NMR (100 MHz, CDCl3) δ 21.19, 21.57, 27.20, 29.00, 35.90, 55.76, 55.87, 69.93, 82.65, 111.07, 112.19, 120.63, 124.06, 128.92, 131.39, 143.45, 147.45, 148.68, 150.33.

Workup

  1. customat room temperature until total consumption of all starting material 13 (20 h)
  2. additionThe reaction mixture was diluted with dichloromethane (10 mL) and aqueous H2SO4 (5%, 10 mL)
  3. extractionAfter the aqueous layer was extracted with CH2Cl2 (2×10 mL)
  4. washwashed successively with diluted aqueous H2SO4 (5%, 10 mL) and brine (10 mL)
  5. dry with materialdried (anhydrous MgSO4)
  6. concentrationconcentrated in vacuo
  7. customto give a yellow oil
  8. customPurification of this crude material
  9. washby elution through a silica gel plug
  10. additiona mixture of ethyl acetate-hexanes (1:2, v/v)

Sources & evidence

ORD record
ord-54e2e7bf944b4ee89f3bd03fcd8d92fe
Source dataset
uspto-grants-2011_11
Patent number
US08058304B2

Reaction notes

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