Acetylene → 1-Azabicyclo[2.2.2]oct-3-yl 2-hydroxy-2-phenyl-3-butynoate

HRID 358253Notes

Reaction equation

HRID 358253 reaction equation
[C:1]1([C:7](=[O:19])[C:8]([O:10][CH:11]2[CH:16]3[CH2:17][CH2:18][N:13]([CH2:14][CH2:15]3)[CH2:12]2)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:20]([Mg]Br)#[CH:21].[Mg].C(Br)C.C#C.[Cl-].[NH4+]>O.C1COCC1>[C:20]([C:7]([C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)([OH:19])[C:8]([O:10][CH:11]1[CH:16]2[CH2:17][CH2:18][N:13]([CH2:14][CH2:15]2)[CH2:12]1)=[O:9])#[CH:21]

Participants

9

Reactant 6

HCID 6326AcetyleneHCID 6332Ethyl BromideHCID 25517Ammonium ChlorideHCID 5462224MagnesiumHCID 190959873-Quinuclidyl phenylglyoxylateHCID 178418486HCID 178418486, compound

Product 1

HCID 3802451-Azabicyclo[2.2.2]oct-3-yl 2-hydroxy-2-phenyl-3-butynoate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

The above ester (13.0 g., 0.5 mole) was dissolved in 500 ml. of THF, cooled to 5° in an ice bath and treated, dropwise with a THF solution of ethynylmagnesium bromide prepared by known procedures from magnesium (1.3 g., 0.055 g. atom), ethyl bromide (5.5 g., 0.05 mole) and excess acetylene. The reaction mixture was stirred at room temperature for 23 hours, and then poured onto 100 ml. of cold water containing 20 g. of ammonium chloride. The mixture was extracted with ether and then with chloroform. The organic extracts were combined, dried and subsequently stripped of volatile components in vacuo to yield 12.0 g. of oil. The product (3.6 g., 25%) was precipitated from the oil by the addition of ether, and melted at 154°-156° C. after recrystallization from hexane. N.m.r. spectroscopy verified the structural assignments.

Workup

  1. additionpoured onto 100 ml
  2. extractionThe mixture was extracted with ether
  3. customdried
  4. customto yield 12.0 g
  5. customThe product (3.6 g., 25%) was precipitated from the oil by the addition of ether, and melted at 154°-156° C.
  6. customafter recrystallization from hexane

Sources & evidence

ORD record
ord-d04625f7b04f4fd1bb94a294fe8abe4a
Source dataset
uspto-grants-1984_08
Patent number
US04465834

Reaction notes

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