Triethylamine → 2-tert-Butyldimethylsilyloxy-9H-fluoren-9-ylideneadamantane

HRID 1722887Notes

Reaction equation

HRID 1722887 reaction equation
[Si:1]([O:8][C:9]1[CH:21]=[CH:20][C:19]2[C:18]3[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=3)[C:12](=O)[C:11]=2[CH:10]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[CH:23]12[CH2:32]C3C[CH:29]([CH2:31][CH:25]([CH2:26]3)[C:24]1=O)[CH2:30]2.[H-].[H-].[H-].[H-].[Li+].[Al+3].C(N([CH2:45][CH3:46])CC)C>C1COCC1>[Si:1]([O:8][C:9]1[CH:21]=[CH:20][C:19]2[C:18]3[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=3)[C:12](=[C:26]3[CH:25]4[CH2:24][CH:23]5[CH2:30][CH:29]([CH2:45][CH:46]3[CH2:32]5)[CH2:31]4)[C:11]=2[CH:10]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 64151AdamantanoneHCID 146455782-tert-Butyldimethylsilyloxy-9H-fluoren-9-oneHCID 21226445Aluminium lithium hydride

Product 1

HCID 146455692-tert-Butyldimethylsilyloxy-9H-fluoren-9-ylideneadamantane

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 2-tert-butyldimethylsilyloxy-9H-fluoren-9-one (0.689 g, 2.2 mmol) and adamantanone (0.66 g, 4.4 mmol) in 30 mL of dry THF was added dropwise over a period of 7 h to a refluxing mixture of TiCl3 (6.8 g, 44 mmol), LAH (0.8 g, 21 mmol) and triethylamine (3 mL) in 80 mL of dry THF. The reaction was refluxed for an additional 12 h. The alkene was then isolated and purified as described above for 1a to give 0.65 g (68%) of 3b: mp 102°-105° C.; 1H NMR (CDCl3) delta 7.832-6.785 (m, 7H), 4.038 (s, 1H), 3.972 (s, 1H), 2.095-1.990 (m, 12H), 1.006 (s, 9H), 0.225 (s, 6H); 13C NMR (CDCl3) delta 159.91, 155.06, 140.64, 139.89, 139.13, 33.61, 126.29, 125.65, 124.31, 119.87, 118.71, 118.43, 116.35, 39.49, 39.40, 36.90, 35.99, 35.90, 27.83, 25.81, 25.73, 18.35, -4.33. ##STR31##

Workup

  1. temperatureThe reaction was refluxed for an additional 12 h

Sources & evidence

ORD record
ord-a0e7264a1424485eafc1cc369763b254
Source dataset
uspto-grants-1989_08
Patent number
US04857652

Reaction notes

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