Methyl 5-(chlorosulfonyl)-4-methoxythiophene-3-carboxylate → HCID 54249985, compound

HRID 1954275Notes

Reaction equation

HRID 1954275 reaction equation
[Br:1][C:2]1[C:11]2[S:12][C:13]([CH3:16])=[C:14]([CH3:15])[C:10]=2[C:9]([C:17]2[CH:22]=[CH:21][C:20]([OH:23])=[C:19]([CH:24]3[CH2:28][CH2:27][CH2:26][CH2:25]3)[CH:18]=2)=[C:8]2[C:3]=1[CH:4]=[CH:5][CH:6]=[CH:7]2.[CH3:29][O:30][C:31]1[C:35]([C:36]([O:38][CH3:39])=[O:37])=[CH:34][S:33][C:32]=1[S:40](Cl)(=[O:42])=[O:41]>[H-].[Na+]>[CH3:39][O:38][C:36]([C:35]1[C:31]([O:30][CH3:29])=[C:32]([S:40]([O:23][C:20]2[CH:21]=[CH:22][C:17]([C:9]3[C:10]4[C:14]([CH3:15])=[C:13]([CH3:16])[S:12][C:11]=4[C:2]([Br:1])=[C:3]4[C:8]=3[CH:7]=[CH:6][CH:5]=[CH:4]4)=[CH:18][C:19]=2[CH:24]2[CH2:28][CH2:27][CH2:26][CH2:25]2)(=[O:41])=[O:42])[S:33][CH:34]=1)=[O:37]

Participants

4

Reactant 2

HCID 2779163Methyl 5-(chlorosulfonyl)-4-methoxythiophene-3-carboxylateHCID 184306982-Cyclopentyl-4-(9-bromo-2,3-dimethyl-naphtho[2,3-b]thiophen-4-yl)-phenol

Product 1

HCID 54249985HCID 54249985, compoundYield 64%

Reagents, catalysts & solvents 1

HCID 24758Sodium hydrideSolvent

Procedure

At ambient temperature, to a stirred solution of 4-(9-bromo-2,3-dimethyl-naphtho[2,3-b]thiophen-4-yl)-2-cyclopentyl-phenol (0.308 g, 0.683 mmol) in N,N-DMF (3.41 mL) was added in one portion 60% NaH/mineral oil (27.3 mg, 0.683 mmol). After 0.5 h, to the reaction was added a solution of commercial 3-methoxy-4-(methoxycarbonyl)thiophene-2-sulphonylchloride (0.204 g, 0.751 mmol) in N,N-DMF (1.37 mL). After 1 h, the reaction was quenched with 1 N HCl (50 mL) combined with product from an identical experiment and extracted with 25% CH2Cl2 /EtOAc. The combined organic extracts were washed with brine (3×), dried (MgSO4) and concentrated. Purification on Biotage KP-Sil eluting with 15% EtOAc/pet. ether gave 0.593 g, (64%) of the title compound as a colorless solid. 1H NMR (DMSO-d6) δ 1.20-1.41 (m, 2 H), 1.43-1.83 (m, 9H), 2.44 (s, 3 H), 3.24 (quintet, 1 H), 3.85 (s, 3 H), 3.99 (s, 3 H), 7.24-7.38 (m, 4 H), 7.50 (t, 1 H), 7.66 (t, 1 H), 8.21 (d, 1 H), 8.81 (s, 1 H).

Workup

  1. waitAfter 1 h
  2. customthe reaction was quenched with 1 N HCl (50 mL)
  3. extractionextracted with 25% CH2Cl2 /EtOAc
  4. washThe combined organic extracts were washed with brine (3×)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated
  7. customPurification on Biotage KP-Sil
  8. washeluting with 15% EtOAc/pet. ether

Sources & evidence

ORD record
ord-54dbdf37a92a4b329ab32c44be65a87e
Source dataset
uspto-grants-2000_09
Patent number
US06121271

Reaction notes

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