p-Toluenesulfonic acid → HCID 178428814, compound

HRID 1791152Notes

Reaction equation

HRID 1791152 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9]1[N:10]([NH2:15])[CH:11]=[CH:12][C:13]=1[CH3:14].CCO/[C:19](/[CH3:26])=[CH:20]/[C:21](OCC)=[O:22].C1(C)C=CC(S(O)(=O)=O)=CC=1>C(Cl)(Cl)Cl>[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9]1[N:10]2[N:15]=[C:19]([CH3:26])[CH:20]=[C:21]([OH:22])[C:11]2=[CH:12][C:13]=1[CH3:14]

Participants

5

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 5354173Ethyl (2E)-3-ethoxy-2-butenoateHCID 220281722-(2,4-dichlorophenyl)-3-methyl-1H-pyrrol-1-amine

Product 1

HCID 178428814HCID 178428814, compound

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

A mixture of 2-(2,4-dichlorophenyl)-3-methyl-1H-pyrrol-1-amine (2.34 g, 9.69 mmol), ethyl trans-3-ethoxycrotonate (1.58 g, 10.0 mmol) and p-toluenesulfonic acid (0.095 g, 0.50 mmol) in CHCl3 (100 mL) is refluxed with a Dean-Stark tube charged with molecular sieves for 24 h. After cooling down to room temperature, the mixture is concentrated in vacuo to dryness and the residue is subjected to column chromatography (silica gel, 1/4 EtOAc/heptane) to give 1.88 g (63%) of light yellow solid as the title compound: mp 234–237° C.; 1H NMR (400 MHz, DMSO-d6) δ 7.76 (d, J=2.1 Hz, 1H), 7.52 (dd, J=2.1, 8.3 Hz, 1H), 7.44 (d, J=8.3 Hz, 1H), 6.49 (s, 1H), 5.94 (s, 1H), 2.20 (s, 3H), 2.10 (s, 3H); 13C NMR (100 MHz, DMSO-d6) δ 153.0, 149.0, 134.2, 135.2, 132.0, 128.2, 127.6, 125.7, 121.2, 119.0, 118.8, 96.0, 92.5, 20.0, 10.5; IR (diffuse reflectance) 3075, 3008, 2997, 2989, 2353, 2327, 2216, 2190, 2105, 1555, 1367, 1314, 1185, 828, 814 cm−1; MS (EI) m/z 308 (M+), 306 (M+); HRMS (FAB) calcd for C15H12Cl2N2O+H 307.0405, found 307.0414; Anal. Calcd for C15H12Cl2N2O: C, 58.65; H, 3.94; N, 9.12. Found: C, 58.68; H, 3.91; N, 8.96.

Workup

  1. temperatureis refluxed with a Dean-Stark tube
  2. additioncharged with molecular sieves for 24 h
  3. concentrationthe mixture is concentrated in vacuo to dryness

Sources & evidence

ORD record
ord-f7540c29e2da4641995f0337818a3512
Source dataset
uspto-grants-2006_07
Patent number
US07074791B2

Reaction notes

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