Water → HCID 59207325, compound

HRID 2242773Notes

Reaction equation

HRID 2242773 reaction equation
[C:1]([CH2:4][CH2:5][CH2:6][CH2:7][C:8]1[CH:13]=[CH:12][C:11]([C:14]2[S:18][C:17]([C:19]3[S:20][C:21]([C:24]4[CH:29]=[CH:28][C:27]([CH2:30][CH2:31][CH2:32][CH2:33][C:34]([OH:36])=[O:35])=[CH:26][CH:25]=4)=[CH:22][CH:23]=3)=[CH:16][CH:15]=2)=[CH:10][CH:9]=1)([OH:3])=[O:2].[CH2:37]=[CH:38][CH:39](O)[CH:40]=[CH2:41].Cl.CN(C)[CH2:46][CH2:47][CH2:48]N=C=NCC.O.CN1C(=O)C[CH2:59][CH2:58]1>CN(C)C1C=CN=CC=1>[CH:38]([CH:39]([O:35][C:34](=[O:36])[CH2:33][CH2:32][CH2:31][CH2:30][C:27]1[CH:26]=[CH:25][C:24]([C:21]2[S:20][C:19]([C:17]3[S:18][C:14]([C:11]4[CH:10]=[CH:9][C:8]([CH2:7][CH2:6][CH2:5][CH2:4][C:1]([O:3][CH:48]([CH:47]=[CH2:46])[CH:58]=[CH2:59])=[O:2])=[CH:13][CH:12]=4)=[CH:15][CH:16]=3)=[CH:23][CH:22]=2)=[CH:29][CH:28]=1)[CH:40]=[CH2:41])=[CH2:37]

Participants

7

Reactant 5

HCID 962WaterHCID 13387N-methyl-2-pyrrolidoneHCID 70204Penta-1,4-dien-3-olHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 59207308HCID 59207308, compound

Product 1

HCID 59207325HCID 59207325, compound

Reagents, catalysts & solvents 1

HCID 142844-(Dimethylamino)pyridineCatalyst

Conditions

Temperature
50 °C

Procedure

5-(4-{5′-[4-(4-Carboxy-butyl)-phenyl]-[2,2′]bithiophenyl-5-yl}-phenyl)-pentanoic acid (1.05 g, 2.02 mmol) and 1,4-pentadien-3-ol (0.42 g, 5.0 mmol) are suspended in NMP (52 mL). 1-(3-Dimethlaminopropyl)-3-ethylcarbodiimide hydrochloride [EDCI] (0.96 g, 5.0 mmol) is added, followed by 4-dimethylaminopyridine (0.61 g, 4.9 mmol) and the mixture is warmed to 50° C. for 10 min. The resulting solution is stirred at room temperature for 3 days. The mixture is poured into water (300 ml) and the resulting precipitate filtered. The solid is dissolved in THF (300 mL), filtered and dry loaded onto silica. The silica is loaded onto a dry silica column and eluted with petrol/dichloromethane (4:1) to remove non-coloured products. The eluent is changed to chloroform and the coloured fractions are collected to afford crude product (1.06 g). A portion (0.5 g) is further purified by reverse phase chromatography (eluent: acetonitrile/THF 9:1 to 1:1, gradient). Final recrystallisation from ethyl acetate afforded the product (0.15 g). 1H NMR (300 MHz, CDCl3): δ (ppm) 7.51 (d, 4H), 7.20 (s, 4H), 7.14 (d, 4H), 5.83 (m, 4H), 5.71 (m, 2H), 5.25 (m, 8H), 2.64 (t, 4H), 2.38 (t,0 4H), 1.73-1.63 (m, 8H); 13C NMR (75 MHz, CDCl3): δ (ppm) 172.4, 143.2, 142.8, 136.4, 135.2, 129.0, 125.6, 125.5, 124.4, 123.4, 117.4, 74.9, 34.9, 34.0, 30.1, 25.9. m.p. (° C.) K 75 SX 174 I.

Workup

  1. filtrationthe resulting precipitate filtered
  2. dissolutionThe solid is dissolved in THF (300 mL)
  3. filtrationfiltered
  4. customdry
  5. washeluted with petrol/dichloromethane (4:1)
  6. customto remove non-coloured products
  7. customthe coloured fractions are collected
  8. customto afford crude product (1.06 g)
  9. customA portion (0.5 g) is further purified by reverse phase chromatography (eluent: acetonitrile/THF 9:1 to 1:1, gradient)
  10. customFinal recrystallisation from ethyl acetate

Sources & evidence

ORD record
ord-ceb6f0580f404b64869bd3561ce7a30f
Source dataset
uspto-grants-2010_03
Patent number
US07674397B2

Reaction notes

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