Cyclopropanecarbonyl chloride → HCID 20353257, compound

HRID 372094Notes

Reaction equation

HRID 372094 reaction equation
[CH2:1]1[CH:5]2[C:6]3[CH:19]=[CH:18][CH:17]=[CH:16][C:7]=3[C:8]3[CH2:15][C:4]2([C:10]2=[CH:11][CH:12]=[CH:13][CH2:14][C:9]=32)[CH2:3][NH:2]1.[O-2].[Mg+2].[CH:22]1([C:25](Cl)=O)[CH2:24][CH2:23]1>>[CH:22]1([CH2:25][N:2]2[CH2:3][C:4]34[CH2:15][CH:8]([C:7]5[CH:16]=[CH:17][CH:18]=[CH:19][C:6]=5[CH:5]3[CH2:1]2)[C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]4=2)[CH2:24][CH2:23]1

Participants

4

Reactant 3

HCID 77637Cyclopropanecarbonyl chlorideHCID 6850729Magnesium monoxideHCID 20353231HCID 20353231, compound

Product 1

HCID 20353257HCID 20353257, compoundYield 82.7%

Procedure

To a slurry of 1.34 g of 2,3,7,12b-tetrahydro-1H-3a,8-methanodibenzo[3,4:6,7]cyclohepta[1,2-c]pyrrole Example 3) and 3 g of magnesium oxide is added 0.93 g of cyclopropanecarbonyl chloride, and the mixture is stirred at room temperature overnight. The filtered mixture is concentrated; the residue is dissolved in methylene chloride, and the solution is washed with base, dried, and concentrated. The residue is heated under reflux with 0.57 g of lithium aluminum hydride in tetrahydrofuran overnight. To the cooled mixture is added, in turn, 0.6 ml of water, 0.6 ml of 15% aqueous sodium hydroxide solution, and 1.8 ml of water; the mixture is filtered, and the filtrate is concentrated to give 1.35 g of 2-cyclopropylmethyl-2,3,8,12b-tetrahydro-1H-3a, 8-methanodibenzo[3,4:6,7]cyclohepta[1,2-c]pyrrole as an oil; nmr spectrum: τ 2.7- 3.2 (m, 8); 6.0-8.0 (m, 8) and 8.8-10.0 (m, 5). It is converted to the hydrochloride which is crystallized from isopropyl alcohol. The melting point of the hydrochloride is erratic and depends upon the rate of heating. Extending drying of the hydrochloride at 120°-130° for 8 hours at 0.1 micron gives a solvent-free product, m.p. 251°-252°, with decomposition.

Workup

  1. concentrationThe filtered mixture is concentrated
  2. dissolutionthe residue is dissolved in methylene chloride
  3. washthe solution is washed with base
  4. customdried
  5. concentrationconcentrated
  6. temperatureThe residue is heated
  7. temperatureunder reflux with 0.57 g of lithium aluminum hydride in tetrahydrofuran overnight
  8. additionTo the cooled mixture is added, in turn, 0.6 ml of water, 0.6 ml of 15% aqueous sodium hydroxide solution, and 1.8 ml of water
  9. filtrationthe mixture is filtered
  10. concentrationthe filtrate is concentrated

Sources & evidence

ORD record
ord-d0fd87480e5f4118963eed10baeac8c2
Source dataset
uspto-grants-1978_05
Patent number
US04088772

Reaction notes

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