1,2-Dichloroethane → N-benzylsulfanylcarbonylmethyl-6-(3,6-dihydroxy-3H-xanthen-9-yl)-isophthalamic acid

HRID 270534Notes

Reaction equation

HRID 270534 reaction equation
C([O:4][CH:5]1[CH:18]=[C:17]2[C:8](=[C:9]([C:23]3[CH:31]=[CH:30][C:26]([C:27]([OH:29])=O)=[CH:25][C:24]=3[C:32]([OH:34])=[O:33])[C:10]3[C:15]([O:16]2)=[CH:14][C:13]([O:19]C(=O)C)=[CH:12][CH:11]=3)[CH:7]=[CH:6]1)(=O)C.C(Cl)CCl.C1C=CC2N(O)N=NC=2C=1.[CH2:49]([S:56][C:57](=[O:60])[CH2:58][NH2:59])[C:50]1[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=1>C1COCC1.CN(C=O)C>[CH2:49]([S:56][C:57]([CH2:58][NH:59][C:27](=[O:29])[C:26]1[CH:25]=[C:24]([C:23]([C:9]2[C:10]3[C:15]([O:16][C:17]4[C:8]=2[CH:7]=[CH:6][CH:5]([OH:4])[CH:18]=4)=[CH:14][C:13]([OH:19])=[CH:12][CH:11]=3)=[CH:31][CH:30]=1)[C:32]([OH:34])=[O:33])=[O:60])[C:50]1[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=1

Participants

7

Reactant 4

HCID 111,2-DichloroethaneHCID 757711-HydroxybenzotriazoleHCID 692105914-(3,6-diacetoxy-3H-xanthen-9-yl)-isophthalic acidHCID 86206484S-benzyl 2-aminoethanethioate

Product 1

HCID 86599707N-benzylsulfanylcarbonylmethyl-6-(3,6-dihydroxy-3H-xanthen-9-yl)-isophthalamic acidYield 64.2%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 13 (0.424 g, 0.92 mmol) in dry THF was added EDC (0.176 g, 0.92 mmol) and HOBt (0.14 g, 0.92 mmol). The solution was stirred for 30 minutes under ice-cold conditions, followed by addition of 8 (0.2523 g, 1.16 mmol) dissolved in minimal amount of DMF. The resulting solution was stirred further for 6 hours at RT. Upon removal of the solvent in vacuo, the residue was taken into ethyl acetate and washed with 1 N HCl (2×30 ml), water (2×30 ml) and brine (2×30 ml). The organic layer was dried over anhydrous Na2SO4 and concentrated under reduced pressure to afford a crude mixture, which was further purified by flash chromatography (silica gel, dichloromethane/methanol=9:1) to afford 2 (0.32 g, 56%). 1H-NMR (300 MHz, CDCl3) δ 8.52 (s, 1H), 8.22 (d, J=8.04 Hz, 1H), 7.25-7.21 (m, 6H), 7.12-7.09 (m, 2H), 6.81-6.75 (m, 4H), 4.39 (d, J=5.61 Hz, 2H), 4.15 (s, 2H), 2.3 (s, 6H). 3C-NMR (60 MHz, DMSO) δ 196.52, 168.78, 168.37, 165.84, 155.31, 152.20, 151.42, 136.72, 134.08, 129.58, 127.74, 127.50, 127.33, 126.45,125.61, 124.50, 123.91, 115.53, 110.46, 82.09, 49.48, 32.90, 20.98. MS (ESI): m/z 623.9 [(M+1)]+.

Workup

  1. stirringThe resulting solution was stirred further for 6 hours at RT
  2. customUpon removal of the solvent in vacuo
  3. washwashed with 1 N HCl (2×30 ml), water (2×30 ml) and brine (2×30 ml)
  4. dry with materialThe organic layer was dried over anhydrous Na2SO4
  5. concentrationconcentrated under reduced pressure
  6. customto afford a crude mixture, which
  7. customwas further purified by flash chromatography (silica gel, dichloromethane/methanol=9:1)

Sources & evidence

ORD record
ord-f72eca9a540f4cbe8b45f38a60ffee08
Source dataset
uspto-grants-2008_11
Patent number
US07449558B2

Reaction notes

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