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Dimethylformamide → 2,2-bis[2-(4-aminophenyl)ethyl]-5-[2-tert-butyl-4-(hydroxymethyl)-5-methyl-phenyl]sulfanyl-4-hydroxy-3H-pyran-6-one

HRID 356545
ノート
印刷プレビュー

反応式

HRID 356545 の反応式
[OH:1][C:2]1[CH2:3][C:4]([CH2:21][CH2:22][C:23]2[CH:28]=[CH:27][C:26]([NH:29]C(=O)[O-])=[CH:25][CH:24]=2)([CH2:9][CH2:10][C:11]2[CH:16]=[CH:15][C:14]([NH:17]C(=O)[O-])=[CH:13][CH:12]=2)[O:5][C:6](=[O:8])[CH:7]=1.[C:33]([C:37]1[CH:42]=[C:41]([CH2:43][OH:44])[C:40]([CH3:45])=[CH:39][C:38]=1[S:46]S(C1C=CC(C)=CC=1)(=O)=O)([CH3:36])([CH3:35])[CH3:34].C([O-])([O-])=O.[K+].[K+].CN(C=O)C>CCOC(C)=O.C(O)(=O)C>[NH2:29][C:26]1[CH:25]=[CH:24][C:23]([CH2:22][CH2:21][C:4]2([CH2:9][CH2:10][C:11]3[CH:12]=[CH:13][C:14]([NH2:17])=[CH:15][CH:16]=3)[O:5][C:6](=[O:8])[C:7]([S:46][C:38]3[CH:39]=[C:40]([CH3:45])[C:41]([CH2:43][OH:44])=[CH:42][C:37]=3[C:33]([CH3:36])([CH3:35])[CH3:34])=[C:2]([OH:1])[CH2:3]2)=[CH:28][CH:27]=1
参加物実験手順後処理出典と根拠反応ノート

参加物

7

反応物 4

HCID 6228DimethylformamideHCID 11430Potassium CarbonateHCID 10499026S-[2-Tert-butyl-4-(hydroxymethyl)-5-methylphenyl] 4-methylbenzenesulfonothioateHCID 86753329(3,6-dihydro-4-hydroxy-6-oxo-2H-pyran-2,2-diyl)bis[2, 1-ethanediyl-(4,1-phenylene)]biscarbamate

生成物 1

HCID 546823122,2-bis[2-(4-aminophenyl)ethyl]-5-[2-tert-butyl-4-(hydroxymethyl)-5-methyl-phenyl]sulfanyl-4-hydroxy-3H-pyran-6-one

試薬・触媒・溶媒 2

HCID 176Acetic Acid溶媒HCID 8857Ethyl Acetate溶媒

実験手順

The title compound was prepared as described in General Method 9 using 0.38 g (0.69 mmol) of (1,1-dimethylethyl)[(3,6-dihydro-4-hydroxy-6-oxo-2H-pyran-2,2-diyl)bis[2,1-ethanediyl-(4,1-phenylene)]biscarbamate prepared in Example OO, 0.35 g (0.96 mmol) of toluene-4-thiosulfonic acid S-(2-tert-butyl-4-hydroxymethyl-5-methyl-phenyl) ester (prepared in Example FFF), 0.58 g (4.2 mmol) of K2CO3, and 5 mL of DMF. The reaction mixture was stirred overnight, and then poured into glacial acetic acid (5 mL) and EtOAc (20 mL). After standard workup, the residue was chromatographed on silica gel, eluting with 1:1 hexane:EtOAc, to give the BOC-protected intermediate. This material was dissolved in CH2 Cl2, cooled in an ice bath, and treated with a steady stream of gaseous HCl for 10 minutes. The solvent was evaporated. The residue was suspended in H2O which was then made basic to pH 11.5 with 10% NaOH and stirred for 20 minutes. The solution was made basic to pH 6.5 with HOAc and extracted with EtOAc (3×50 mL). The combined extracts were washed with brine, dried (MgSO4), and concentrated to give the title compound, m.p. 144°-146° C. 1H NMR (DMSO-d6) δ 1.43 (s, 9 H), 1.81 (s, 3 H), 1.95 (m, 4 H), 2.42 (m, partially obscured by DMSO, 4 H), 2.87 (br s, 2 H), 4.30 (s, 2 H), 4.90 (br s, 1 H), 6.45 (d, 4 H), 6.65 (s, 1 H), 6.80 (d, 4 H), 7.20 (s, 1 H).

後処理

  1. customAfter standard workup, the residue was chromatographed on silica gel
  2. washeluting with 1:1 hexane

出典と根拠

ORDレコード
ord-2aa0ccdc47bb448e8120d96ebc25f4dd
出典データセット
uspto-grants-1998_11
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US05834506

反応ノート

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