Phosphorus oxychloride → 6-Ethynylspiro[4.5]dec-6-ene

HRID 1471371Notes

Reaction equation

HRID 1471371 reaction equation
[C:1]([C:3]1(O)[CH2:12][CH2:11][CH2:10][CH2:9][C:4]21[CH2:8][CH2:7][CH2:6][CH2:5]2)#[CH:2].O=P(Cl)(Cl)Cl>N1C=CC=CC=1>[C:1]([C:3]1[C:4]2([CH2:9][CH2:10][CH2:11][CH:12]=1)[CH2:8][CH2:7][CH2:6][CH2:5]2)#[CH:2]

Participants

4

Reactant 2

HCID 24813Phosphorus oxychlorideHCID 866475806-Ethynylspiro[4.5]decan-6-ol

Product 1

HCID 866475816-Ethynylspiro[4.5]dec-6-eneYield 76.7%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Conditions

Temperature
87.5 °C

Procedure

At 20-27° C., a solution of 6-ethynylspiro[4.5]decan-6-ol (180 g, 1 mol) in pyridine (1 l) was treated dropwise with POCl3 (207 g, 2 mol). The resulting mixture was heated for 5.5 h heating at 85-90° C., poured into ice and extracted twice with pentane (800 and 300 ml). The combined organic phases were washed twice with water (500 ml), with a saturated aqueous solution of NaCl (300 ml), dried (MgSO4), and concentrated. Short-path Vigreux-distillation (8 mbar, head temperature: 85° C.) of the crude product (146 g) gave 6-ethynylspiro[4.5]dec-6-ene (122.9 g, 76%).

Workup

  1. temperatureThe resulting mixture was heated for 5.5 h
  2. additionpoured into ice
  3. extractionextracted twice with pentane (800 and 300 ml)
  4. washThe combined organic phases were washed twice with water (500 ml), with a saturated aqueous solution of NaCl (300 ml)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated
  7. distillationShort-path Vigreux-distillation (8 mbar, head temperature: 85° C.) of the crude product (146 g)

Sources & evidence

ORD record
ord-55372eea9f4e47cb86bea93b0edd0ea8
Source dataset
uspto-grants-2015_04
Patent number
US09012391B2

Reaction notes

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