3-Amino-9-ethylcarbazole → Methyl 4-[(9-ethylcarbazol-3-yl)amino]-5-methylthiothiophene-2-carboxylate

HRID 2298689Notes

Reaction equation

HRID 2298689 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:8]([O:10][CH3:11])=[S:9])[S:5][C:6]=1[CH3:7].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+].[NH2:64][C:65]1[CH:66]=[CH:67][C:68]2[N:69]([CH2:78][CH3:79])[C:70]3[C:75]([C:76]=2[CH:77]=1)=[CH:74][CH:73]=[CH:72][CH:71]=3>C1(C)C=CC=CC=1>[CH2:78]([N:69]1[C:68]2[CH:67]=[CH:66][C:65]([NH:64][C:2]3[CH:3]=[C:4]([C:8]([O:10][CH3:11])=[S:9])[S:5][C:6]=3[CH3:7])=[CH:77][C:76]=2[C:75]2[C:70]1=[CH:71][CH:72]=[CH:73][CH:74]=2)[CH3:79]

Participants

6

Reactant 4

HCID 85883-Amino-9-ethylcarbazoleHCID 10796Cesium carbonateHCID 634876Binap, (A+-)-HCID 86583861Methyl 4-bromo-5-methylthiothiophene-2-carboxylate

Product 1

HCID 86758695Methyl 4-[(9-ethylcarbazol-3-yl)amino]-5-methylthiothiophene-2-carboxylateYield 47%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

The same procedure as in Example 254, step (a) was followed using 120 mg (0.449 mmol) of methyl 4-bromo-5-methylthiothiophene-2-carboxylate (as prepared in Example 241, step (a), 41 mg (10 mol %) of tris-(dibenzylidineacetone)dipalladium, 42 mg (15 mol %) of racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, 205 mg (0.629 mmol) of cesium carbonate and 118 mg (0.56 mmol) of 3-amino-9-ethylcarbazole in 900 μL of toluene, and chromatographed as before using 40% CH2Cl2-hexane to afford 80 mg (47%) of the title compound as a yellow resin. 1H-NMR (CDCl3, 400 MHz) δ1.46 (t, 3H, J=7.2 Hz), 2.44 (s, 3H), 3.85 (s, 3H), 4.39 (q, 2H, J=7.2 Hz), 6.25 (s, 1H), 7.24 (m, 1H), 7.28 (s, 1H), 7.40 (m, 2H), 7.49 (m, 1H), 7.61 (s, 1H), 7.83 (d, 1H, J=2.1 Hz), 8.06 (d, 1H), J=7.8 Hz).

Workup

  1. customchromatographed as

Sources & evidence

ORD record
ord-b54e857ff3fd4dacaa2ae8c454b55c96
Source dataset
uspto-grants-2002_12
Patent number
US06492403B1

Reaction notes

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