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

HRID 270534ノート

反応式

HRID 270534 の反応式
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

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

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)]+.

後処理

  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)

出典と根拠

ORDレコード
ord-f72eca9a540f4cbe8b45f38a60ffee08
出典データセット
uspto-grants-2008_11
特許番号
US07449558B2

反応ノート

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