Dichloromethane → 3-(Ethoxycarbonyl)-4-(1,5-dimethoxypent-3-yl)pyrrole

HRID 222562Notes

Reaction equation

HRID 222562 reaction equation
[CH3:1][O:2][CH2:3][CH2:4][CH:5]([CH2:13][CH2:14][O:15][CH3:16])[CH:6]=[CH:7][C:8]([O:10][CH2:11][CH3:12])=[O:9].CC1C=CC(S([CH2:27][N+:28]#[C-:29])(=O)=O)=CC=1.[H-].[Na+].C(Cl)Cl>CS(C)=O.CCOCC.CCOCC.[Cl-].[Na+].O>[CH2:11]([O:10][C:8]([C:7]1[C:6]([CH:5]([CH2:13][CH2:14][O:15][CH3:16])[CH2:4][CH2:3][O:2][CH3:1])=[CH:29][NH:28][CH:27]=1)=[O:9])[CH3:12]

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 24758Sodium hydrideHCID 161915Tosylmethyl isocyanideHCID 76645421Ethyl 6-methoxy-4-(2-methoxyethyl)-hex-2-enoate

Product 1

HCID 578598413-(Ethoxycarbonyl)-4-(1,5-dimethoxypent-3-yl)pyrroleYield 74%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 19869614Ether dimethylsulfoxideSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

A solution of 24 (3.00 g, 13.03 mmol) and TosMIC (2.54 g, 13.02 mmol) in DMSO/Et2O (1:2, 25 mL) was added via cannula to a vigorously stirred suspension of NaH (649 mg, 27.04 mmol) in Et2O (11.3 mL) under argon. Stirring was continued for 3 h. Brine and CH2Cl2 were added in small portions. The aqueous layer was extracted with CH2Cl2. The organic extract was washed with brine. The solvent was removed at reduced pressure. The oily residue was chromatographed [silica, CH2Cl2/ethyl acetate (9:1)] to yield a pale yellow oil (2.59 g, 74%): 1H NMR δ 1.32 (t, J=7.2 Hz, 3H), 1.88-1.95 (m, 4H), 3.26-3.33 (m, 10H), 4.24 (q, J=7.2 Hz, 2H), 6.54 (s, 1H), 7.37 (s, 1H), 8.74 (br, 1H); 13C NMR δ 14.59, 30.35, 36.04, 58.50, 59.47, 71.65, 114.69, 116.66, 124.92, 129.05, 165.28; FAB-MS obsd 270.1703, calcd 270.1705 [(M+H)+, M=C14H23NO4].

Workup

  1. extractionThe aqueous layer was extracted with CH2Cl2
  2. extractionThe organic extract
  3. washwas washed with brine
  4. customThe solvent was removed at reduced pressure
  5. customThe oily residue was chromatographed [silica, CH2Cl2/ethyl acetate (9:1)]

Sources & evidence

ORD record
ord-19ecd2f262114cc8a853451ea9d320f2
Source dataset
uspto-grants-2012_06
Patent number
US08207329B2

Reaction notes

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