2-Thiophenecarbonyl chloride → HCID 71230583, compound

HRID 2199578Notes

Reaction equation

HRID 2199578 reaction equation
[CH3:1][O:2][C:3](=[O:25])[CH2:4][C:5]1[CH:9]=[CH:8][S:7][C:6]=1[C:10]1[S:14][C:13]([C:15]2[S:16][CH:17]=[CH:18][C:19]=2[CH2:20][C:21]([O:23][CH3:24])=[O:22])=[CH:12][CH:11]=1.[S:26]1[CH:30]=[CH:29][CH:28]=[C:27]1[C:31](Cl)=[O:32].[Al+3].[Cl-].[Cl-].[Cl-]>C(Cl)Cl>[CH3:24][O:23][C:21](=[O:22])[CH2:20][C:19]1[CH:18]=[C:17]([C:31]([C:27]2[S:26][CH:30]=[CH:29][CH:28]=2)=[O:32])[S:16][C:15]=1[C:13]1[S:14][C:10]([C:6]2[S:7][CH:8]=[CH:9][C:5]=2[CH2:4][C:3]([O:2][CH3:1])=[O:25])=[CH:11][CH:12]=1

Participants

5

Reactant 3

HCID 789282-Thiophenecarbonyl chlorideHCID 6451240Aluminum(III) ChlorideHCID 71231148HCID 71231148, compound

Product 1

HCID 71230583HCID 71230583, compoundYield 34%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Intermediate C (146 mg, 0.372 mmol) was dissolved in dry CH2Cl2 (3 ml), 2-thiophenecarbonyl chloride (92 μL, 0.856 mmol) and AlCl3 (114 mg, 0.856 mmol) were added and the mixture was sealed under Ar-atmosphere. After 26 hrs, the reaction was diluted with CH2Cl2 (10 ml), washed with water (20 ml) and the aqueous layer was subsequently washed with CH2Cl2 (10 ml×2). The organic layers were combined and evaporated to dryness to obtain the crude product. The residue was purified by flash chromatography using toluene/EtOAc (19:1→9:1→6:1) as eluent to first obtain the monoacylated product methyl 2-(2-{5-[3-(2-methoxy-2-oxoethyl)-5-(thiophene-2-carbonyl)thiophen-2-yl]thiophen-2-yl}thiophen-3-yl)acetate Yield: 63 mg (34%). 1H NMR (400 MHz, CDCl3): δ 3.75 (s, 3H), 3.77 (s, 3H), 3.81 (s, 2H), 3.87 (s, 2H), 7.08 (d, J 4.0 Hz, 1H), 7.20-7.23 (m, 2H), 7.29-7.31 (m, 2H), 7.72 (dd, J 2.0, 4.0 Hz, 1H), 7.87 (s, 1H), 7.94 (dd, J 2.0, 4.0 Hz, 1H). Second eluted compound; the diacylated product methyl 2-(2-{5-[3-(2-methoxy-2-oxoethyl)-5-(thiophene-2-carbonyl)thiophen-2-yl]thiophen-2-yl}-5-(thiophene-2-carbonyl)thiophen-3-yl)acetate. Yield: 90 mg (39%) 1H NMR (400 MHz, CDCl3): δ 3.79 (s, 6H), 3.87 (s, 4H), 7.23 (dd, J 4.0, 4.0 Hz, 2H), 7.36 (s, 2H), 7.73 (dd, J 2.0, 4.0 Hz, 2H), 7.88 (s, 2H), 7.94 (dd, J 2.0, 4.0, 2H).

Workup

  1. customthe mixture was sealed under Ar-atmosphere
  2. washwashed with water (20 ml)
  3. washthe aqueous layer was subsequently washed with CH2Cl2 (10 ml×2)
  4. customevaporated to dryness
  5. customto obtain the crude product
  6. customThe residue was purified by flash chromatography

Sources & evidence

ORD record
ord-041dc181b042467dabf8e7d1a440e640
Source dataset
uspto-grants-2016_06
Patent number
US09359311B2

Reaction notes

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