Methyl Isocyanate → 20-(5,5-dimethyl-1,3-dioxan-2-yl)-1alpha,2alpha-epoxy-7alpha-(N-methylcarbamoyloxy)pregn-5-en-3beta-yl acetate

HRID 1708752Notes

Reaction equation

HRID 1708752 reaction equation
[C:1]([O:4][C@H:5]1[C@@H:31]2[O:32][C@@H:30]2[C@@:29]2([CH3:33])[C:7](=[CH:8][C@@H:9]([OH:35])[C@@H:10]3[C@@H:28]2[CH2:27][CH2:26][C@@:25]2([CH3:34])[C@H:11]3[CH2:12][CH2:13][C@@H:14]2[CH:15]([CH:17]2[O:22][CH2:21][C:20]([CH3:24])([CH3:23])[CH2:19][O:18]2)[CH3:16])[CH2:6]1)(=[O:3])[CH3:2].[CH3:36][N:37]=[C:38]=[O:39].C(OCC)(=O)C.CCCCCC>C1(C)C=CC=CC=1.N1C=CC=CC=1>[C:1]([O:4][C@H:5]1[C@@H:31]2[O:32][C@@H:30]2[C@@:29]2([CH3:33])[C:7](=[CH:8][C@@H:9]([O:35][C:38](=[O:39])[NH:37][CH3:36])[C@@H:10]3[C@@H:28]2[CH2:27][CH2:26][C@@:25]2([CH3:34])[C@H:11]3[CH2:12][CH2:13][C@@H:14]2[CH:15]([CH:17]2[O:18][CH2:19][C:20]([CH3:23])([CH3:24])[CH2:21][O:22]2)[CH3:16])[CH2:6]1)(=[O:3])[CH3:2]

Participants

6

Reactant 3

HCID 12228Methyl IsocyanateHCID 21226206Ethyl acetate hexaneHCID 8674580220-(5,5-Dimethyl-1,3-dioxan-2-yl)-1alpha, 2alpha-epoxy-7alpha-hydroxypregna-5-en-3beta-yl acetate

Product 1

HCID 8846371220-(5,5-dimethyl-1,3-dioxan-2-yl)-1alpha,2alpha-epoxy-7alpha-(N-methylcarbamoyloxy)pregn-5-en-3beta-yl acetateYield 65%

Reagents, catalysts & solvents 2

HCID 1049PyridineCatalystHCID 1140TolueneSolvent

Conditions

Temperature
60 °C

Procedure

In 5 ml of toluene was dissolved 49.0 mg (0.1 mmole) of 20-(5,5-dimethyl-1,3-dioxan-2-yl)-1α,2α-epoxy-7α-hydroxypregna-5-en-3β-yl acetate, followed by addition of one drop of pyridine. Then, 0.1 ml (1.7 mmoles) of methyl isocyanate was added at a temperature of 0° C. and the mixture was stirred at a temperature of 60° C. for 30 minutes. The reaction mixture thus obtained was cooled to room temperature, poured in ice-water, and extracted 3 times with 20 ml portions of methylene chloride. The extracts are pooled, washed successively with water and aqueous sodium chloride solution, and dried over magnesium sulfate. The solvent was then distilled off under reduced pressure. Finally the residue was purified by silica gel chromatography (eluent:ethyl acetate-hexane=1:10, v/v) to recover 35 mg of 20-(5,5-dimethyl-1,3-dioxan-2-yl)-1α,2α-epoxy-7α-(N-methylcarbamoyloxy)pregn-5-en-3β-yl acetate (yield: 65%).

Workup

  1. customThe reaction mixture thus obtained
  2. temperaturewas cooled to room temperature
  3. extractionextracted 3 times with 20 ml portions of methylene chloride
  4. washwashed successively with water and aqueous sodium chloride solution
  5. dry with materialdried over magnesium sulfate
  6. distillationThe solvent was then distilled off under reduced pressure
  7. customFinally the residue was purified by silica gel chromatography (eluent

Sources & evidence

ORD record
ord-c480639c4dad4acb96a2b01e22df38fe
Source dataset
uspto-grants-1994_10
Patent number
US05359055

Reaction notes

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