Pyridine → 5-Methoxy-4-[2-methyl-3-(3-methyl-2-butenyl)oxiranyl]-6-[3-(methylcarbamoyloxy)propylcarbamoyloxy]-1-oxaspiro[2,5]octane

HRID 1031602Notes

Reaction equation

HRID 1031602 reaction equation
[OH:1][CH2:2][CH2:3][CH2:4][NH:5][C:6]([O:8][CH:9]1[CH2:16][CH2:15][C:12]2([O:14][CH2:13]2)[CH:11]([C:17]2([CH3:25])[CH:19]([CH2:20][CH:21]=[C:22]([CH3:24])[CH3:23])[O:18]2)[CH:10]1[O:26][CH3:27])=[O:7].[N:28]1[CH:33]=CC=C[CH:29]=1.Cl[C:35]([O:37][C:38]1[CH:43]=[CH:42][C:41]([N+:44]([O-:46])=[O:45])=[CH:40][CH:39]=1)=[O:36].CN>ClCCl.C(OCC)C.CO>[CH3:27][O:26][CH:10]1[CH:9]([O:8][C:6](=[O:7])[NH:5][CH2:4][CH2:3][CH2:2][O:1][C:35]([O:37][C:38]2[CH:39]=[CH:40][C:41]([N+:44]([O-:46])=[O:45])=[CH:42][CH:43]=2)=[O:36])[CH2:16][CH2:15][C:12]2([O:14][CH2:13]2)[CH:11]1[C:17]1([CH3:25])[CH:19]([CH2:20][CH:21]=[C:22]([CH3:24])[CH3:23])[O:18]1.[CH3:27][O:26][CH:10]1[CH:9]([O:8][C:6](=[O:7])[NH:5][CH2:4][CH2:3][CH2:2][O:1][C:29](=[O:36])[NH:28][CH3:33])[CH2:16][CH2:15][C:12]2([O:14][CH2:13]2)[CH:11]1[C:17]1([CH3:25])[CH:19]([CH2:20][CH:21]=[C:22]([CH3:24])[CH3:23])[O:18]1

Participants

9

Reactant 4

HCID 1049PyridineHCID 6329MethylamineHCID 821294-Nitrophenyl chloroformateHCID 149888816-(3-Hydroxypropylcarbamoyloxy)-5-methoxy-4-[2-methyl-3-(3-methyl-2-butenyl)oxiranyl]-1-oxaspiro[2,5]octane

Product 2

HCID 149888825-Methoxy-4-[2-methyl-3-(3-methyl-2-butenyl)oxiranyl]-6-[3-(methylcarbamoyloxy)propylcarbamoyloxy]-1-oxaspiro[2,5]octaneYield 160.2%HCID 216201735-Methoxy-4-[2-methyl-3-(3-methyl-2-butenyl)oxiranyl]-6-(4-nitrophenoxycarbonyloxypropylcarbamoyloxy)-1-oxaspiro[2,5]octane

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Procedure

To a mixture of 6-(3-hydroxypropylcarbamoyloxy)-5-methoxy-4-[2-methyl-3-(3-methyl-2-butenyl)oxiranyl]-1-oxaspiro[2,5]octane (15 mg) and pyridine (12.3 mg) in dichloromethane (1 ml) was added portionwise 4-nitrophenyl chloroformate (32 mg) at ambient temperature. After stirring for 2 hours, 5-methoxy-4-[2-methyl-3-(3-methyl-2-butenyl)oxiranyl]-6-(4-nitrophenoxycarbonyloxypropylcarbamoyloxy)-1-oxaspiro[2,5]octane was prepared in the reaction mixture. To the mixture, 30% methanol solution of methylamine (7 mg) was added in one portion. The mixture was stirred for 1 hour at ambient temperature and diluted with diethyl ether (5 ml). The solution was washed with brine, 1N aqueous hydrochloric acid, 1N aqueous sodium hydroxide, and brine successively. The solvent was dried and evaporated in vacuo to give a crude oil, which was purified by column chromatography on silica gel eluted by diethyl ether to yield 5-methoxy-4-[2-methyl-3-(3-methyl-2-butenyl)oxiranyl]-6-[3-(methylcarbamoyloxy)propylcarbamoyloxy]-1-oxaspiro[2,5]octane (13.8 mg) as crystals.

Workup

  1. stirringThe mixture was stirred for 1 hour at ambient temperature
  2. washThe solution was washed with brine, 1N aqueous hydrochloric acid, 1N aqueous sodium hydroxide, and brine successively
  3. customThe solvent was dried
  4. customevaporated in vacuo
  5. customto give a crude oil, which
  6. customwas purified by column chromatography on silica gel
  7. washeluted by diethyl ether

Sources & evidence

ORD record
ord-6d17b1b52aa74ab1836ec000f3c4686b
Source dataset
uspto-grants-1990_09
Patent number
US04954496

Reaction notes

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