Dichloromethane → 5,5-Dimethyl-10-[5-(piperidino)valeryloxy]-8-(3-methyl-2-octyl)-2-(2-propynyl)-1,2,3,4-tetrahydro-5H-[1]benzopyrano[3,4-d] pyridine hydrochloride

HRID 441877Notes

Reaction equation

HRID 441877 reaction equation
[CH3:1][C:2]1([CH3:29])[C:21]2[CH2:22][CH2:23][N:24]([CH2:26][C:27]#[CH:28])[CH2:25][C:20]=2[C:5]2[C:6]([OH:19])=[CH:7][C:8]([CH:10]([CH:12]([CH3:18])[CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])[CH3:11])=[CH:9][C:4]=2[O:3]1.Cl.[N:31]1([CH2:37][CH2:38][CH2:39][CH2:40][C:41](O)=[O:42])[CH2:36][CH2:35][CH2:34][CH2:33][CH2:32]1.C1(N=C=NC2CCCCC2)CCCCC1.C(Cl)[Cl:60]>C(Cl)Cl.C1CCCCC1.CO.C(Cl)(Cl)Cl>[ClH:60].[CH3:29][C:2]1([CH3:1])[C:21]2[CH2:22][CH2:23][N:24]([CH2:26][C:27]#[CH:28])[CH2:25][C:20]=2[C:5]2[C:6]([O:19][C:41](=[O:42])[CH2:40][CH2:39][CH2:38][CH2:37][N:31]3[CH2:36][CH2:35][CH2:34][CH2:33][CH2:32]3)=[CH:7][C:8]([CH:10]([CH:12]([CH3:18])[CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])[CH3:11])=[CH:9][C:4]=2[O:3]1

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 10868DicyclohexylcarbodiimideHCID 990408-(1,2-Dimethylheptyl)-1,3,4,5-tetrahydro-5,5-dimethyl-2-(2-propyn-1-yl)-2H-(1)benzopyrano(4,3-c)pyridin-10-olHCID 545927615-(Piperidin-1-yl)pentanoic acid hydrochloride

Product 1

HCID 214181445,5-Dimethyl-10-[5-(piperidino)valeryloxy]-8-(3-methyl-2-octyl)-2-(2-propynyl)-1,2,3,4-tetrahydro-5H-[1]benzopyrano[3,4-d] pyridine hydrochloride

Reagents, catalysts & solvents 2

HCID 21584188Chloroform methanolSolventHCID 21916607Dichloromethane cyclohexaneSolvent

Procedure

A mixture of 2.4 g. (6.06 mm.) of 5,5-dimethyl-10-hydroxy-8-(3-methyl-2-octyl)-2-(2-propynyl)-1,2,3,4-tetrahydro-5H-[1]benzopyrano[3,4-d]pyridine, 1.35 g. (6.06 mm.) of δ-piperidinovaleric acid hydrochloride and 1.30 g. (6.30 mm.) of dicyclohexylcarbodiimide in 100 ml. of methylene chloride was stirred at room temperature for 5 hours. The reaction mixture was cooled overnight in the refrigerator and the by-product of dicyclohexylurea removed by suction filtration. The mother liquor was evaporated to give a golden, viscous residue which was dissolved in a mixture of methylene chloride/cyclohexane and allowed to stand in the cold for 2 hours. Gravity filtration separated a small amount of solid which had appeared, and the solvents were removed using a rotary evaporator. Crystallization from methylene chloride/diethyl ether gave 2.5 g. (69%) of colorless crystals, m.p. 140°-144° C., The sample was pure by thin layer chromatography (10% MeOH/CHCl3) and the infrared and nuclear magnetic resonance spectra were in agreement with the proposed structure.

Workup

  1. additionA mixture of 2.4 g
  2. temperatureThe reaction mixture was cooled overnight in the refrigerator
  3. customthe by-product of dicyclohexylurea removed by suction filtration
  4. customThe mother liquor was evaporated
  5. customto give a golden, viscous residue which
  6. customcold for 2 hours
  7. filtrationGravity filtration
  8. customseparated a small amount of solid which
  9. customthe solvents were removed
  10. customa rotary evaporator
  11. customCrystallization from methylene chloride/diethyl ether
  12. customgave 2.5 g

Sources & evidence

ORD record
ord-5a2548ed704d4fe89c68b50a2846d217
Source dataset
uspto-grants-1977_08
Patent number
US04042694

Reaction notes

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