Allyl bromide → HCID 20608122, compound

HRID 430598Notes

Reaction equation

HRID 430598 reaction equation
Cl.Cl.N[CH:4]1[CH:9]2[CH2:10][CH2:11][N:6]([CH2:7][CH2:8]2)[CH2:5]1.C([O-])([O-])=[O:13].[Na+].[Na+].[CH2:18](Br)[CH:19]=[CH2:20].C(NC[CH2:27][CH3:28])CC>C(O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C(OCC)C.O>[C:11]1(=[O:13])[C:10]2[C:9]3[CH:8]=[CH:7][CH:27]=[CH:28][C:4]=3[CH:20]=[CH:19][C:18]=2[CH2:5][NH:6]1

Participants

9

Reactant 4

HCID 7841Allyl bromideHCID 8902DipropylamineHCID 10340Sodium CarbonateHCID 197853Quinuclidine, 3-amino-, dihydrochloride

Product 1

HCID 20608122HCID 20608122, compoundYield 34%

Reagents, catalysts & solvents 4

HCID 178418476HCID 178418476, compoundCatalystHCID 702EthanolSolvent2×HCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Procedure

A suspension of 11.2 g (56 mmoles) of 3-aminoquinuclidine dihydrochloride, 22 g (207 mmoles) of anhydrous Na2CO3, and 300 ml of ethanol was heated under reflux in an inert atmosphere with vigorous stirring for 1 h and was then cooled to ambient temperature and supplemented with 4.8 ml (55 mmoles) of allyl bromide. The mixture was allowed to react with stirring at ambient temperature for 20 min. and then heated under reflux for 1 h and finally supplemented with 14.6 g (50 mmoles) of 2-bromomethyl-1-naphthalene methyl carboxylate (prepared as described in the synthesis method of Example 1) dissolved in the minimum quantity of ethanol. The resulting mixture was heated under reflux for 12 h. The solvent was evaporated under reduced pressure and the residue was taken up with 500 ml of dimethyl formamide. The solid which had not dissolved was filtered out and the filtrate was supplemented with 40 ml (292 mmoles) of dipropylamine and 0.5 g (0.71 mmoles) of Pd(PPh3)2Cl2. The resulting mixture was heated to 100° C. for about 30 minutes in an inert nitrogen atmosphere and then poured into water and ice and extracted with CHCl3. The extracts were washed thoroughly with water, dehydrated over sodium sulphate and evaporated at reduced pressure. The semi-solid residue which was obtained was solidified as a result of repeated washings with ethyl ether. 5.1 g of pure, solid, microcrystalline Compound 6 was thus obtained. Yield 34%. Melting point 138-141° C. 1H NMR (CDCl3): 1.59-1.96 (m, 4H), 2.20 (m, 1H), 2.89-3.18 (m, 5H), 3.41 (m, 1H), 4.48 (t, J=8.3, 1H), 4.64 (m, 2H), 7.49-7.68 (m, 3H), 7.90 (d, J=8.1, 1H), 7.98 (d, J=8.4, 1H), 9.20 (d, J=8.3, 1H).

Workup

  1. temperaturewas heated
  2. temperatureunder reflux in an inert atmosphere
  3. customto react
  4. stirringwith stirring at ambient temperature for 20 min.
  5. temperatureheated
  6. temperatureunder reflux for 1 h
  7. customprepared
  8. customas described in the synthesis method of Example 1)
  9. temperatureThe resulting mixture was heated
  10. temperatureunder reflux for 12 h
  11. customThe solvent was evaporated under reduced pressure
  12. dissolutionThe solid which had not dissolved
  13. filtrationwas filtered out
  14. temperatureThe resulting mixture was heated to 100° C. for about 30 minutes in an inert nitrogen atmosphere
  15. extractionextracted with CHCl3
  16. washThe extracts were washed thoroughly with water
  17. customevaporated at reduced pressure
  18. customThe semi-solid residue which was obtained

Sources & evidence

ORD record
ord-10fd7e98f5454a7aab41c66d2c89146d
Source dataset
uspto-grants-2001_11
Patent number
US06323216B1

Reaction notes

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