Triethylamine → HCID 89781034, compound

HRID 2369446Notes

Reaction equation

HRID 2369446 reaction equation
[Br:1][C:2]1[CH:15]=[CH:14][C:13]2[S:12][C:11]3[C:6](=[CH:7][C:8]([NH:16][CH3:17])=[CH:9][CH:10]=3)[C:5](=[O:18])[C:4]=2[CH:3]=1.C(N(CC)CC)C.[CH3:26][O:27][C:28]([C:30]1[CH:31]=[CH:32][C:33]2[C:37]([Cl:38])=[C:36]([C:39](Cl)=[O:40])[S:35][C:34]=2[CH:42]=1)=[O:29]>C(Cl)Cl.CN(C1C=CN=CC=1)C>[CH3:26][O:27][C:28]([C:30]1[CH:31]=[CH:32][C:33]2[C:37]([Cl:38])=[C:36]([C:39](=[O:40])[N:16]([C:8]3[CH:9]=[CH:10][C:11]4[S:12][C:13]5[C:4](=[CH:3][C:2]([Br:1])=[CH:15][CH:14]=5)[C:5](=[O:18])[C:6]=4[CH:7]=3)[CH3:17])[S:35][C:34]=2[CH:42]=1)=[O:29]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 89780650HCID 89780650, compoundHCID 89780755HCID 89780755, compound

Product 1

HCID 89781034HCID 89781034, compoundYield 60%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Procedure

To 0.51 g (1.6 mmol) of 2-bromo-7-methylamino-thioxanthen-9-one (14) and 10 mL of triethylamine in 15 mL of anhyd CH2Cl2 was added 0.61 g (2.1 mmol) of 3-chloro-2-chlorocarbonyl-benzo[b]thiophene-6-carboxylic acid methyl ester (12) dissolved in 10 mL of anhyd CH2Cl2 at 5-8° C. in an ice bath. A catalytic amount of DMAP was added. The reaction mixture was warmed at room temperature and stirred for 48 h under N2. The reaction mixture was filtered to remove triethylamine hydrochloride salt, the filtrate was washed three times with aq saturated NaHCO3, H2O, three times with aq. 2N HCl to remove unreacted amines, H2O, brine, dried over Na2SO4, and concentrated in vacuo to give crude ester 10. The crude ester 10 was chromatographed on silica gel, eluting with 20% ethyl acetate in hexane to give 0.55 g (60% yield) of NMR pure 10 (LG−=Cl−) as a brown powder, mp 237-239° C. Found: C, 52.09; H, 2.64; N, 2.47%; calcd for C25H15NO4S2ClBr: C, 52.40; H, 2.62; N, 2.44%; 1H-NMR (400 MHz, CDCl3): 3.61 (3H, s), 3.92 (3H, s), 7.35-7.54 (3H, m), 7.66-7.80 (2H, m), 8.02 (1H, d, J=8.2 Hz), 8.40 (1H, s), 8.51 (1H, s), 8.69 (1H, s); 13C-NMR (100 MHz, CDCl3): 38.3, 52.6, 120.8, 120.9, 122.8, 124.9, 126.3, 127.3, 127.4, 127.8, 128.6, 129.6, 130.0, 131.0, 132.7, 134.1, 135.8, 136.1, 137.6, 138.7, 141.4, 162.5, 166.5, 178.1.

Workup

  1. filtrationThe reaction mixture was filtered
  2. customto remove triethylamine hydrochloride salt
  3. washthe filtrate was washed three times with aq saturated NaHCO3, H2O, three times with aq. 2N HCl
  4. customto remove unreacted amines, H2O, brine
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated in vacuo
  7. customto give crude ester 10
  8. customThe crude ester 10 was chromatographed on silica gel
  9. washeluting with 20% ethyl acetate in hexane
  10. customto give 0.55 g (60% yield) of NMR pure 10 (LG−=Cl−) as a brown powder, mp 237-239° C

Sources & evidence

ORD record
ord-934bc98973984f27a65fa5907142e829
Source dataset
uspto-grants-2014_04
Patent number
US08703970B2

Reaction notes

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