Propyne → HCID 22602329, compound

HRID 2308402Notes

Reaction equation

HRID 2308402 reaction equation
CN(C)CCN(C)C.[CH:9]#[C:10][CH3:11].[Li]CCCC.Br[CH2:18][CH2:19][CH:20]([CH3:30])[CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH3:29].[Cl-].[NH4+]>CN(P(N(C)C)(N(C)C)=O)C.C1COCC1.C1COCC1>[CH3:30][CH:20]([CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH3:29])[CH2:19][CH2:18][C:9]#[C:10][CH3:11]

Participants

8

Reactant 5

HCID 6335PropyneHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 25517Ammonium ChlorideHCID 15569719HCID 15569719, compoundHCID 178418339Butyllithium

Product 1

HCID 22602329HCID 22602329, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 86583969tetrahydrofuran HMPASolvent

Conditions

Temperature
0 °C

Procedure

Tetramethylethylenediamine (TMEDA) (15 ml) was added to a THF (80 ml) solution of propyne (about 4 g, 0.1 mol) under argon. To the mixture, n-BuLi (1.55 M, 64.5 ml, 100 mmols) was added dropwise at −78° C. With the temperature being raised gradually to 0° C., the mixture was stirred for 1.5 hours, and then cooled again to −78° C. Thereto, an HMPA-THF (20 ml+20 ml) solution of the 1-bromo-3-methyldodecane (5″) (13.2 g, 50 mmols) was added dropwise, and with the temperature of the mixture being raised gradually to room temperature, stirring was continued overnight. The reaction mixture was poured into a saturated aqueous solution of ammonium chloride, and extracted with hexane. The resulting organic layer was washed (water, a saturated aqueous solution of sodium bicarbonate, a saturated aqueous solution of sodium chloride), dried (magnesium sulfate), and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to obtain 6-methyl-2-pentadecyne (6″) (12.1 g, 97%). 1H-NMR (90 MHz, CDCl3) 0.84 (3H,d,J=7,6-Me), 0.88 (3H,t,J=7,15-H), 1.0-1.6 (19H,m,5˜14-H), 1.77 (3H,t,J=2.5,1-H), 2.12 (2H,m,4-H).

Workup

  1. temperaturecooled again to −78° C
  2. temperaturewith the temperature of the mixture being raised gradually to room temperature
  3. stirringstirring
  4. waitwas continued overnight
  5. extractionextracted with hexane
  6. washThe resulting organic layer was washed (water
  7. dry with materiala saturated aqueous solution of sodium bicarbonate, a saturated aqueous solution of sodium chloride), dried (magnesium sulfate)
  8. concentrationconcentrated under reduced pressure
  9. customThe resulting residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-bf57764a195b41289db301d74f6ab7b2
Source dataset
uspto-grants-2004_12
Patent number
US06835846B2

Reaction notes

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