Pyridine → Ethyl 5-(4-(((9H-fluoren-9-yl)methoxy)carbonylamino)phenylthio)-4-nitrothiophene-2-carboxylate

HRID 605374Notes

Reaction equation

HRID 605374 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([S:8][C:9]2[S:13][C:12]([C:14]([O:16][CH2:17][CH3:18])=[O:15])=[CH:11][C:10]=2[N+:19]([O-:21])=[O:20])=[CH:4][CH:3]=1.[CH:22]1[C:34]2[CH:33]([CH2:35][O:36][C:37](Cl)=[O:38])[C:32]3[C:27](=[CH:28][CH:29]=[CH:30][CH:31]=3)[C:26]=2[CH:25]=[CH:24][CH:23]=1.N1C=CC=CC=1>C(Cl)Cl>[CH:22]1[C:34]2[CH:33]([CH2:35][O:36][C:37]([NH:1][C:2]3[CH:3]=[CH:4][C:5]([S:8][C:9]4[S:13][C:12]([C:14]([O:16][CH2:17][CH3:18])=[O:15])=[CH:11][C:10]=4[N+:19]([O-:21])=[O:20])=[CH:6][CH:7]=3)=[O:38])[C:32]3[C:27](=[CH:28][CH:29]=[CH:30][CH:31]=3)[C:26]=2[CH:25]=[CH:24][CH:23]=1

Participants

5

Reactant 3

HCID 1049PyridineHCID 343679-Fluorenylmethyl chloroformateHCID 67040833Ethyl 5-(4-aminophenylthio)-4-nitrothiophene-2-carboxylate

Product 1

HCID 67040709Ethyl 5-(4-(((9H-fluoren-9-yl)methoxy)carbonylamino)phenylthio)-4-nitrothiophene-2-carboxylateYield 100%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A suspension of the product of Example 430B (0.500 g, 1.541 mmol) and 9-fluorenylmethoxycarbonyl chloride (0.478 g, 1.849 mmol) in methylene chloride (10 mL) under a nitrogen atmosphere was treated with pyridine (0.25 mL, 3.083 mmol), and the resulting solution stirred for 18 hours at room temperature. The reaction was diluted with methylene chloride (50 mL) and washed with 1N aqueous HCl (50 mL) then water (50 mL). The organic was dried over magnesium sulfate, filtered, and concentrated by rotary evaporation. Purification by silica gel flash chromatography eluting with methylene chloride afforded the title compound as a bright yellow solid (0.842 g, quantitative). 1H NMR (300 MHz, DMSO-D6) δ ppm 1.23 (t, J=7.17 Hz, 3 H) 4.24 (q, J=7.23 Hz, 2 H) 4.35 (t, J=6.43 Hz, 1 H) 4.57 (d, J=6.25 Hz, 2 H) 7.29-7.50 (m, 4 H) 7.69 (s, 4 H) 7.77 (d, J=7.35 Hz, 2 H) 7.92 (d, J=7.35 Hz, 2 H) 8.11 (s, 1 H) 10.15 (s, 1 H); MS (ESI+) m/z 564 (M+NH4)+, 569 (M+Na)+.

Workup

  1. washwashed with 1N aqueous HCl (50 mL)
  2. dry with materialThe organic was dried over magnesium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated by rotary evaporation
  5. customPurification by silica gel flash chromatography
  6. washeluting with methylene chloride

Sources & evidence

ORD record
ord-373641299b014b3ba492f834d8658aeb
Source dataset
uspto-grants-2011_03
Patent number
US07910595B2

Reaction notes

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