3-Hydroxy-2,2-dimethylpropionaldehyde → (Z)-2,2-dimethyl-3-dodecen-1-ol

HRID 1388647Notes

Reaction equation

HRID 1388647 reaction equation
[Br-].[CH2:2]([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH3:10].O1CCCCC1OC1CCCCO1.[CH3:43][C:44]([CH:48]=O)([CH2:46][OH:47])[CH3:45].C([Li])CCC>CCCCCC.CN(P(N(C)C)(N(C)C)=O)C.C1COCC1>[CH3:43][C:44]([CH3:45])(/[CH:48]=[CH:2]\[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH3:10])[CH2:46][OH:47]

Participants

8

Reactant 4

HCID 116993-Hydroxy-2,2-dimethylpropionaldehydeHCID 263182Tetrahydropyranyl etherHCID 2724864Phosphonium, nonyltriphenyl-, bromide (1:1)HCID 178418339Butyllithium

Product 1

HCID 86739260(Z)-2,2-dimethyl-3-dodecen-1-olYield 85%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolventHCID 12679HexamethylphosphoramideSolvent

Procedure

A 5.6 g (11.9 mmoles) sample of (n-nonyl)triphenylphosphonium bromide was coupled with 1.86 g (10 mmoles) of the tetrahydropyranyl ether of hydroxypivaldehyde using the Wittig reaction conditions described in the previous examples (THF:HMPT, 2:1; 7 ml of 1.6 M n-butyllithium in hexane; -78° C.). The crude product (3.4 g) was chromatographed on silica gel. Hexane-ether (7:3) eluted 2.8 g (95%) of (Z)-2,2-dimethyl-3-dodecen-1-ol tetrahydropyranyl ether, which was dissolved in 28 ml of methanol and subsequently treated with 0.3 ml of 2 N HCl. After stirring for 3 hours at room temperature, most of the solvent (about 20 ml) was removed in vacuo, and the residue was extracted with ether. The ethereal solution was washed with brine, saturated NaHCO3 solution, brine, dried over MgSO4, and the solvent was evaporated under reduced pressure. The crude alcohol (2.2 g) was chromatographed on silica gel to afford 1.8 g (85%) of (Z)-2,2-dimethyl- 3-dodecen-1-ol as an oil.

Workup

  1. customthe Wittig reaction conditions
  2. customThe crude product (3.4 g) was chromatographed on silica gel
  3. washHexane-ether (7:3) eluted 2.8 g (95%) of (Z)-2,2-dimethyl-3-dodecen-1-ol tetrahydropyranyl ether, which
  4. dissolutionwas dissolved in 28 ml of methanol
  5. additionsubsequently treated with 0.3 ml of 2 N HCl
  6. customwas removed in vacuo
  7. extractionthe residue was extracted with ether
  8. washThe ethereal solution was washed with brine, saturated NaHCO3 solution, brine
  9. dry with materialdried over MgSO4
  10. customthe solvent was evaporated under reduced pressure
  11. customThe crude alcohol (2.2 g) was chromatographed on silica gel

Sources & evidence

ORD record
ord-d761e21cb9ea4060b04814b243e1776a
Source dataset
uspto-grants-1984_02
Patent number
US04432906

Reaction notes

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