Triphenylphosphine → 17-Ethyl-1-hydroxy-12-[2'-(4"-amino-3"-propyloxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9]octacos-18-ene-2,3,10,16-tetraone

HRID 248278Notes

Reaction equation

HRID 248278 reaction equation
[CH2:1]([CH:3]1[CH:29]=[C:28]([CH3:30])[CH2:27][CH:26]([CH3:31])[CH2:25][CH:24]([O:32][CH3:33])[CH:23]2[O:34][C:19]([OH:38])([CH:20]([CH3:37])[CH2:21][CH:22]2[O:35][CH3:36])[C:18](=[O:39])[C:17](=[O:40])[N:16]2[CH:11]([CH2:12][CH2:13][CH2:14][CH2:15]2)[C:10](=[O:41])[O:9][CH:8]([C:42]([CH3:57])=[CH:43][CH:44]2[CH2:49][CH2:48][CH:47]([N:50]=[N+]=[N-])[CH:46]([O:53][CH2:54][CH2:55][CH3:56])[CH2:45]2)[CH:7]([CH3:58])[CH2:6][CH2:5][C:4]1=[O:59])[CH3:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1C=CC=CC=1>[OH-:9].[NH4+:16].[CH2:1]([CH:3]1[CH:29]=[C:28]([CH3:30])[CH2:27][CH:26]([CH3:31])[CH2:25][CH:24]([O:32][CH3:33])[CH:23]2[O:34][C:19]([OH:38])([CH:20]([CH3:37])[CH2:21][CH:22]2[O:35][CH3:36])[C:18](=[O:39])[C:17](=[O:40])[N:16]2[CH:11]([CH2:12][CH2:13][CH2:14][CH2:15]2)[C:10](=[O:41])[O:9][CH:8]([C:42]([CH3:57])=[CH:43][CH:44]2[CH2:49][CH2:48][CH:47]([NH2:50])[CH:46]([O:53][CH2:54][CH2:55][CH3:56])[CH2:45]2)[CH:7]([CH3:58])[CH2:6][CH2:5][C:4]1=[O:59])[CH3:2]

Participants

5

Reactant 2

HCID 11776TriphenylphosphineHCID 5709641317-Ethyl-1-hydroxy-12-[2'-(4"-azido-3"-propyloxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9]octacos-18-ene-2,3,10,16-tetraone

Product 2

HCID 14923Ammonium HydroxideYield 2%HCID 5699537717-Ethyl-1-hydroxy-12-[2'-(4"-amino-3"-propyloxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9]octacos-18-ene-2,3,10,16-tetraoneYield 166.1%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of 17-ethyl-1-hydroxy-12-[2'-(4"-azido-3"-propyloxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9 ]octacos-18-ene-2,3,10,16-tetraone (46 mg) in 10% aqueous benzene (900 μl) was added triphenylphosphine (29 mg) and the mixture heated to 70° C. with stirring. After 6.5 hours, the stir bar was removed and the reaction cooled to room temperature. The mixture was concentrated to 10% volume in vacuo and applied directly to a column of silica gel for purification by flash chromatography (ethyl acetate: hexane (1:1)+1% methanol then 2% ammonium hydroxide, 5% methanol in methylene chloride) to give the title compound (37 mg).

Workup

  1. customthe stir bar was removed
  2. temperaturethe reaction cooled to room temperature
  3. concentrationThe mixture was concentrated to 10% volume in vacuo
  4. customapplied directly to a column of silica gel for purification by flash chromatography (ethyl acetate: hexane (1:1)+1% methanol

Sources & evidence

ORD record
ord-7885dd5a0dc041bd9c8842c62542382b
Source dataset
uspto-grants-1993_05
Patent number
US05208228

Reaction notes

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