Iodine → HCID 178438795、化合物

HRID 253612

反応式

HRID 253612 の反応式
[C:1]([NH2:5])([CH3:4])([CH3:3])[CH3:2].[CH2:6]([CH:9]1[CH2:14][CH2:13][C:12](=O)[CH2:11][CH2:10]1)[CH2:7][CH3:8].[Cl:16][C:17]1[CH:18]=[CH:19][C:20]([O:28][CH3:29])=[C:21]([CH:27]=1)[C:22]([N:24]=[C:25]=[S:26])=[O:23].II.C(=O)(O)[O-].[Na+]>CCCCCC.[Ti](Cl)(Cl)(Cl)Cl.C(OCC)C.N1C=CC=CC=1.CO>[C:1]([N:5]1[C:12]2[CH2:11][CH2:10][CH:9]([CH2:6][CH2:7][CH3:8])[CH2:14][C:13]=2/[C:25](=[N:24]/[C:22](=[O:23])[C:21]2[CH:27]=[C:17]([Cl:16])[CH:18]=[CH:19][C:20]=2[O:28][CH3:29])/[S:26]1)([CH3:4])([CH3:3])[CH3:2]

参加物

11

反応物 5

HCID 807IodineHCID 6385Tert-ButylamineHCID 1424824-PropylcyclohexanoneHCID 516892Sodium BicarbonateHCID 167716985-Chloro-2-methoxybenzoyl isothiocyanate

生成物 1

HCID 178438795HCID 178438795、化合物収率 20%

試薬・触媒・溶媒 5

HCID 24193Titanium Tetrachloride触媒HCID 887Methanol溶媒HCID 1049Pyridine溶媒HCID 3283Diethyl Ether溶媒HCID 8058Hexane溶媒

実験手順

To a solution of tert-butylamine (366 mg, 5 mmol) in anhydrous hexane (20 mL) at 0° C. was added titanium(IV) chloride (133 mg, 0.5 mmol). After 5 min, the cooling bath was removed and 4-propylcyclohexanone (140 mg, 1 mmol) was added in one portion. The resulting mixture was stirred at ambient temperature for 2 h. Then, the precipitated solid was filtered and washed with anhydrous ethyl ether. The filtrate and washings were combined and concentrated under reduced pressure. The residue was dissolved in THF (20 mL) and treated with 5-chloro-2-methoxybenzoyl isothiocyanate (190 mg, 0.83 mmol) for 1 h at room temperature. Iodine (211 mg, 0.83 mmol) was added followed by addition of MeOH (10 mL) and pyridine (1 mL). The mixture was allowed to stir at room temperature for additional 2 h and then saturated sodium bicarbonate solution and ethyl ether were added. The mixture was stirred for 30 min, the ether layer was separated and the aqueous solution was extracted with ethyl ether. The ether extracts were combined, washed with brine, dried with anhydrous MgSO4 and concentrated under reduced pressure. The residue was twice evaporated with toluene and acetonitrile and then purified by chromatography (hexane-EtOAc 1:1) to afford 70 mg of the title compound. 1H NMR (300 MHz, DMSO-d6) δ ppm 0.85-1.02 (m, 3H), 1.29-1.53 (m, 6H), 1.68 (s, 9H), 1.90-2.07 (m, 1H), 2.19 (dd, J=15.9, 10.2 Hz, 1H), 2.78-3.01 (m, 2H), 3.09-3.26 (m, 1H), 3.72-3.84 (m, 3H), 7.11 (d, J=8.8 Hz, 1H), 7.45 (dd, J=8.8, 3.1 Hz, 1H), 7.68 (d, J=3.1 Hz, 1H); MS (DCI/NH3) m/z 421 (M+H)+. Anal. calcd for C22H29ClN2O2S.0.1H2O: C, 62.50; H, 6.96; N, 6.63. Found: C, 62.21; H, 6.99; N, 6.49.

後処理

  1. customthe cooling bath was removed
  2. filtrationThen, the precipitated solid was filtered
  3. washwashed with anhydrous ethyl ether
  4. concentrationconcentrated under reduced pressure
  5. dissolutionThe residue was dissolved in THF (20 mL)
  6. stirringto stir at room temperature for additional 2 h
  7. stirringThe mixture was stirred for 30 min
  8. customthe ether layer was separated
  9. extractionthe aqueous solution was extracted with ethyl ether
  10. washwashed with brine
  11. dry with materialdried with anhydrous MgSO4
  12. concentrationconcentrated under reduced pressure
  13. customThe residue was twice evaporated with toluene and acetonitrile
  14. custompurified by chromatography (hexane-EtOAc 1:1)

出典と根拠

ORDレコード
ord-580aec49e0a548e7b80b8d0e028f4d58
出典データセット
uspto-grants-2011_01
特許番号
US07872033B2

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