Diethyl Ether → HCID 88366201, compound

HRID 1648685Notes

Reaction equation

HRID 1648685 reaction equation
[H-].C([Al+]CC(C)C)C(C)C.[O:11]([CH2:29][C:30]1[CH:31]=[C:32]([CH:36]([CH2:39]/[CH:40]=[C:41](/[C:43]2[CH:52]=[CH:51][C:50]3[C:49]([CH3:54])([CH3:53])[CH2:48][CH2:47][C:46]([CH3:56])([CH3:55])[C:45]=3[CH:44]=2)\[CH3:42])[C:37]#N)[CH:33]=[CH:34][CH:35]=1)[Si:12]([C:25]([CH3:28])([CH3:27])[CH3:26])([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C([O:59]CC)C>>[O:11]([CH2:29][C:30]1[CH:31]=[C:32]([CH:36]([CH2:39]/[CH:40]=[C:41](/[C:43]2[CH:52]=[CH:51][C:50]3[C:49]([CH3:54])([CH3:53])[CH2:48][CH2:47][C:46]([CH3:56])([CH3:55])[C:45]=3[CH:44]=2)\[CH3:42])[CH:37]=[O:59])[CH:33]=[CH:34][CH:35]=1)[Si:12]([C:25]([CH3:28])([CH3:27])[CH3:26])([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

4

Reactant 3

HCID 3283Diethyl EtherHCID 21225700DiisobutylaluminumhydrideHCID 88366316HCID 88366316, compound

Product 1

HCID 88366201HCID 88366201, compoundYield 97%

Procedure

Diisobutylaluminum hydride (1.0M in hexanes, 1.54 mL, 1.54 mmol) was added dropwise to a solution of 26 (0.74 g, 1.18 mmol) in anhydrous diethyl ether (22 mL) at 0° C. under argon. The reaction mixture was allowed to warm to room temperature over 2.5 h. The reaction was quenched with ethyl acetate (2.5 mL) and 1N H2SO4 solution (5 mL) and stirring was continued for 10 min. The mixture was poured into a separatory funnel and the layers were separated. The aqueous layer was extracted again with diethyl ether. The organic layers were combined, washed sequentially with 1N NaOH solution and saturated sodium chloride solution, and concentrated in vacuo to give 0.72 g (97%) of 27 as a dark yellow oil. 1H NMR showed the presence of trace impurities, but the compound decomposed on silica gel. The material was used without purification in the next reaction. 1H NMR (300 MHz, CDCl3) δ9.73 (s, 1H, CHO), 7.61-7.77 (m, 4H, ArH), 7.03-7.42 (m, 13H, ArH), 5.62 (t, J=9 Hz, 1H, CH=C), 4.78 (s, 2H, CH2OSi), 3.66 (t, J=6 Hz, 1H, CHCHO), 2.92-3.01 (m, 1H, 1×CH2CH), 2.55-2.67 (m, 1H, 1×CH2CH), 1.95 (s, 3H, C=CCH3), 1.66 (s, 4H, CH2CH2), 1.28 (s, 12H, 4×CH3), and 1.07 (s, 9H, SiC(CH3)3).

Workup

  1. customThe reaction was quenched with ethyl acetate (2.5 mL) and 1N H2SO4 solution (5 mL)
  2. additionThe mixture was poured into a separatory funnel
  3. customthe layers were separated
  4. extractionThe aqueous layer was extracted again with diethyl ether
  5. washwashed sequentially with 1N NaOH solution and saturated sodium chloride solution
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-09ae3e6c4191438da6d726e930a280a7
Source dataset
uspto-grants-1995_07
Patent number
US05436369

Reaction notes

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