Oxygen → 6-Heptyn-1-ol

HRID 1160644Notes

Reaction equation

HRID 1160644 reaction equation
[OH:1][CH2:2][C:3]#[C:4][CH2:5][CH2:6][CH2:7][CH3:8].[OH:9][CH2:10][CH2:11][C:12]#[C:13][CH2:14][CH2:15][CH3:16].[OH:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][C:23]#[CH:24].O=O>N1C=CC=CC=1.CO.Cl[Cu]>[OH:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][C:7]#[CH:8].[OH:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][C:15]#[C:16][C:24]#[C:23][CH2:22][CH2:21][CH2:20][CH2:19][CH2:18][OH:17]

Participants

8

Reactant 4

HCID 977OxygenHCID 846933-Heptyn-1-olHCID 5351112-Heptyn-1-olHCID 110078496-Heptyn-1-ol2×

Product 2

HCID 110078496-Heptyn-1-olHCID 111278826,8-Tetradecadiyne-1,14-diol

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 22021344Pyridine methanolSolvent

Procedure

HO(CH2)5C≡CH was prepared by the KAPA-promoted isomerization of HOCH2C≡C(CH2)3CH3 (prepared according to Millar, J. G.; Oehlschlager, A. C. J. Org. Chem. 1984, 49, 2332-2338) or HO(CH2)2C≡C(CH2)2CH3 (commercially available GFS Chemicals; Powell, Ohio). Oxidative coupling of HO(CH2)5C≡CH was carried out in a glass reaction vessel by dissolving 6.95 grams of HO(CH2)5C≡CH in pyridine/methanol (2.0 milliliters/6.2 milliliters) and adding 307 grams of CuCl followed by stirring in the presence of oxygen until all the staring material was consumed. The reaction mixture was worked up with diethyl ether and 4N HCl, the combined organic layers were dried over MgSO4, filtered and concentrated. Recrystallization of the residue from 1/1 hexanes/tert-butyl methyl ether to yield 5.35 grams of HO(CH2)5C≡C—C≡C(CH2)5OH as a pink solid.

Workup

  1. customprepared
  2. customwas consumed
  3. dry with materialthe combined organic layers were dried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customRecrystallization of the residue from 1/1 hexanes/tert-butyl methyl ether

Sources & evidence

ORD record
ord-c6fa6497c8754c6aae419390de5f66d9
Source dataset
uspto-grants-2010_10
Patent number
US07816473B2

Reaction notes

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