Diisopropylamine → HCID 86604548, compound

HRID 1795699Notes

Reaction equation

HRID 1795699 reaction equation
[Li]CC[CH2:4][CH3:5].C(N[CH:10]([CH3:12])[CH3:11])(C)C.S1C2C=CC=CC=2N=C1S([CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33])(=O)=O.[C:34]([O:37][CH:38]1C(OC(OCC)C)(C)C[CH2:41][CH:42]([O:57][CH:58]([O:60][CH2:61][CH3:62])[CH3:59])[CH2:43][C:44]([O:46][CH:47](/[C:52](/[CH3:56])=[CH:53]/[CH:54]=O)[CH:48]([CH3:51])[CH:49]=[CH:50]1)=[O:45])(=[O:36])[CH3:35].[Cl-].[NH4+]>CCCCCC.O1CCCC1.C(OCC)(=O)C>[C:34]([O:37][CH:38]1[C:10]([O:36][CH:34]([O:37][CH2:4][CH3:5])[CH3:35])([CH3:11])[CH2:12][CH2:41][CH:42]([O:57][CH:58]([O:60][CH2:61][CH3:62])[CH3:59])[CH2:43][C:44]([O:46][CH:47](/[C:52](/[CH3:56])=[CH:53]/[CH:54]=[CH:33][CH2:32][CH2:31][CH2:30][CH2:29][CH2:28][CH2:27][CH2:26][CH3:25])[CH:48]([CH3:51])[CH:49]=[CH:50]1)=[O:45])(=[O:36])[CH3:35]

Participants

9

Reactant 5

HCID 7912DiisopropylamineHCID 25517Ammonium ChlorideHCID 22185919HCID 22185919, compoundHCID 67057055HCID 67057055, compound2×HCID 178418339Butyllithium

Product 1

HCID 86604548HCID 86604548, compoundYield 38%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 1.57 M n-BuLi in hexane (0.17 mL) was added dropwise to a solution of diisopropylamine (31 mg, 0.36 mmol) in tetrahydrofuran (1.8 mL) at −78° C., followed by stirring at the same temperature for 20 min. To the resulting solution, a solution of 1,3-benzothiazol-2-ylnonylsulfone (44 mg, 0.14 mmol) in tetrahydrofuran (1 mL) at −78° C., followed by stirring at the same temperature for 30 min. 0.6 mL of the resulting solution (which corresponds to 8.8 mg, 0.027 mmol of the anion of 1,3-benzothiazol-2-ylnonylsulfone) was added to asolution of (8E,12E)-7-acetoxy-3,6-bis(1-ethoxyethoxy)-6,10,12-trimethyl-14-oxotetradeca-8,12-dien-11-olide (6.9 mg, 0.013 mmol) in tetrahydrofuran (0.5 mL) at −78° C. The temperature of the resulting solution was gradually (during one hour 50 min.) raised to room temperature with stirring. A saturated aqueous ammonium chloride solution was added to the reaction mixture and the mixture was further diluted with ethyl acetate. Then, the mixture was washed with brine, dried over anhydrous magnesium sulfate and evaporated. The resulting crude product was purified by silica gel column chromatography (Kanto silica gel 60N, spherical, neutral, 40 to 100 μm, eluate; hexane:ethyl acetate=80:20) to give the title compound (3.2 mg, 38%) as a pale yellow oil.

Workup

  1. customat −78° C.
  2. stirringby stirring at the same temperature for 30 min
  3. custom(during one hour 50 min.)
  4. stirringwith stirring
  5. washThen, the mixture was washed with brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customevaporated
  8. customThe resulting crude product was purified by silica gel column chromatography (Kanto silica gel 60N, spherical, neutral, 40 to 100 μm, eluate; hexane:ethyl acetate=80:20)

Sources & evidence

ORD record
ord-df64ab29ef7041ee8903ce992c7f8544
Source dataset
uspto-grants-2006_04
Patent number
US07026352B1

Reaction notes

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