Iodine → HCID 21519713, compound

HRID 1283298Notes

Reaction equation

HRID 1283298 reaction equation
[Mg].II.C(Br)C.[CH3:7][N:8]1[CH2:13][CH2:12][CH:11](Cl)[CH2:10][CH2:9]1.[CH:15]12[C:27](=[O:28])[CH:19]3[C:20]4[CH:26]=[CH:25][CH:24]=[CH:23][C:21]=4[CH:22]1[CH:16]2[C:17]1[CH:32]=[CH:31][CH:30]=[CH:29][C:18]=13.[Cl-].[NH4+]>O1CCCC1>[OH:28][C:27]1([CH:11]2[CH2:12][CH2:13][N:8]([CH3:7])[CH2:9][CH2:10]2)[CH:19]2[C:18]3[CH:29]=[CH:30][CH:31]=[CH:32][C:17]=3[CH:16]3[CH:15]1[CH:22]3[C:21]1[CH:23]=[CH:24][CH:25]=[CH:26][C:20]=12

Participants

8

Reactant 6

HCID 807IodineHCID 6332Ethyl BromideHCID 25517Ammonium ChlorideHCID 793424-chloro-N-methylpiperidineHCID 5462224Magnesium2×HCID 12117541HCID 12117541, compound

Product 1

HCID 21519713HCID 21519713, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

In a reaction vessel, 1.95 g (0.08 mole) of magnesium chips under dry nitrogen is covered with 12 ml of abs. tetrahydrofuran, and corroded with a trace of iodine and 0.1 ml of ethylbromide. While stirring is maintained, 10.7 g (0.08 mole) of 1-methyl-4-chloropiperidine, dissolved in 30 ml of abs. tetrahydrofuran, is added dropwise at 60° in such a manner that the reaction mixture remains boiling. Refluxing is performed for a further 30 minutes until all the magnesium is dissolved. To this Grignard solution cooled to 5° is then added dropwise at 5-10° in the course of 30 minutes, with stirring, 4.46 g (0.02 mole) of 1,1a,6,10b-tetrahydro-1,6-methano-dibenzo[a,e]cyclopropa[c]cyclohepten-11-one dissolved in 20 ml of abs. tetrahydrofuran. The reaction mixture is subsequently heated to ca. 20° and then stirred into 350 ml of a 3% ammonium chloride solution. The reaction product precipitated in crystalline form is filtered off with suction, washed with water and dried in a water-jet vacuum at ca. 50° to obtain 4-(11-hydroxy-1,1a,6,10b-tetrahydro-1,6-methano-dibenzo[a,e]cyclopropa[c]cyclohepten-11-yl)-1-methyl-piperidine; M.P. 239°-242°.

Workup

  1. temperatureis maintained
  2. temperatureRefluxing
  3. temperatureTo this Grignard solution cooled to 5°
  4. additionis then added dropwise at 5-10° in the course of 30 minutes
  5. stirringwith stirring
  6. temperatureThe reaction mixture is subsequently heated to ca. 20°
  7. customThe reaction product precipitated in crystalline form
  8. filtrationis filtered off with suction
  9. washwashed with water
  10. dry with materialdried in a water-jet vacuum at ca. 50°

Sources & evidence

ORD record
ord-e13350f828604103819ceb9f9370a363
Source dataset
uspto-grants-1976_08
Patent number
US03974284

Reaction notes

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