CID 406 → Lithium diisopropylamide

HRID 1647836Notes

Reaction equation

HRID 1647836 reaction equation
P(=O)([O-])[O-].[CH:5]([NH:8][CH:9]([CH3:11])[CH3:10])([CH3:7])[CH3:6].[Li+:12].CCC[CH2-].[C:17]12([C:27]3[CH:28]=[C:29]([CH:32]=[CH:33][C:34]=3[O:35][CH3:36])[CH:30]=[O:31])[CH2:26][CH:21]3[CH2:22][CH:23]([CH2:25][CH:19]([CH2:20]3)[CH2:18]1)[CH2:24]2>C1COCC1>[CH:5]([N-:8][CH:9]([CH3:11])[CH3:10])([CH3:7])[CH3:6].[Li+:12].[C:17]12([C:27]3[CH:28]=[C:29]([CH:32]=[CH:33][C:34]=3[O:35][CH3:36])[CH:30]=[O:31])[CH2:18][CH:19]3[CH2:25][CH:23]([CH2:22][CH:21]([CH2:20]3)[CH2:26]1)[CH2:24]2

Participants

7

Reactant 4

HCID 406CID 406HCID 7912DiisopropylamineHCID 61028n-Butyl lithiumHCID 540295304-Methoxy-3-tricyclo[3.3.1.13,7]dec-1-ylbenzaldehyde

Product 2

HCID 2724682Lithium diisopropylamideHCID 540295304-Methoxy-3-tricyclo[3.3.1.13,7]dec-1-ylbenzaldehyde

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

11.42 g (30.51 mmoles) of the phosphonate obtained in Example II(b) are dissolved in 50 ml of THF. This solution is then cooled to -78° C. and there is slowly added thereto a solution of lithium di-isopropylamide which was prepared in a conventional manner starting with 3.4 g (33.58 mmoles) of di-isopropylamine and 2.1 ml (33.56 mmole) of a solution of N-butyllithium (1.6M in hexane). The red-orange solution thus obtained is stirred for 30 minutes at -78° C. and a suspension of 3-(1-adamantyl)-4-methoxybenzaldehyde obtained above in part (a) (7.5 g; 27.74 mmoles) in 140 ml of THF is added in fractions thereto. This addition lasts for about 10 minutes. The reaction mixture is then stirred initially for 20 minutes at -78° C. and then for 2 hours at 25° C. The mixture is poured into water and extracted three times with 100 ml of ethylether. The organic phase is washed with a saturated solution of sodium chloride, dried over magnesium sulfate, filtered and the solvents evaporated. The residue in chromatographed on a silica column, as in Example II(c), yielding a mixture of two isomers, E and Z, of the methyl ester of p-[1-(2,2-dimethoxyethyl)-2-[3-(1-adamantyl)-4-methoxyphenyl]-vinyl] benzoic acid (7.5 g, 53% yield) in the form of a partially crystallized light yellow oil. This mixture is used as such in the continuation of the synthesis.

Workup

  1. additionthere is slowly added
  2. customThe red-orange solution thus obtained

Sources & evidence

ORD record
ord-67e666a6282a43588ca9fa1f6037f284
Source dataset
uspto-grants-1995_07
Patent number
US05434180

Reaction notes

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