Ethyl formate → HCID 54066486, compound

HRID 1032629Notes

Reaction equation

HRID 1032629 reaction equation
[H-].[Na+].[C:3]1(=[O:15])[CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4]1.C(OCC)=O.C1(C)C=CC(S([N:30]=[N+:31]=[N-])(=O)=O)=CC=1>C(OCC)C.C(O)C.O>[N+:30](=[C:4]1[CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][C:3]1=[O:15])=[N-:31]

Participants

8

Reactant 4

HCID 8025Ethyl formateHCID 13246CyclododecanoneHCID 13661p-Toluenesulfonyl azideHCID 24758Sodium hydride2×

Product 1

HCID 54066486HCID 54066486, compoundYield 43.6%

Reagents, catalysts & solvents 3

HCID 702EthanolCatalystHCID 962WaterSolventHCID 3283Diethyl EtherSolvent3×

Procedure

A suspension of 1.3 gm (33 mmole) of sodium hydride dispersion (60%) in 12 mL of diethyl ether and one drop of absolute ethanol was cooled in an ice bath under nitrogen. A mixture was prepared of 2.0 gm (11 mmole) cyclododecanone and 2.4 gm (33 mmole of ethyl formate in 20 mL of diethyl ether. This second solution was added, dropwise, to the sodium hydride suspension. The resulting mixture was stirred in the ice bath for about 3 hours after which time it was allowed to come to room temperature. After stirring at room temperature overnight, a solution of 3.99 gm (33 mmole) p-toluenesulfonyl azide in 25 mL of diethyl ether was added dropwise. The resulting mixture was stirred at room temperature for about 3 hours. Ten mL of water was added and the organic layer removed. This organic layer was then washed with 100 mL of 10% NaOH. The aqueous layer was extracted with three portions of ethyl acetate. The combined organic phases were dried over sodium sulfate and then concentrated in vacuo (less than 30° C.). The residue was subjected to flash chromatography on 40 microns silica gel to give 1.0 gm of 2-diazocyclododecan-1-one as a bright yellow-orange solid, MP 43°-44° C. Elemental analysis calculated for C12H20N2O: C: 69.19; H: 9.68; N: 13.45. Found: C: 69.13; H: 9.69; N: 13.57. Pmr, cmr, ir, and UV spectra consistent with the desired product were obtained.

Workup

  1. additionThis second solution was added
  2. customto come to room temperature
  3. stirringThe resulting mixture was stirred at room temperature for about 3 hours
  4. customthe organic layer removed
  5. washThis organic layer was then washed with 100 mL of 10% NaOH
  6. extractionThe aqueous layer was extracted with three portions of ethyl acetate
  7. dry with materialThe combined organic phases were dried over sodium sulfate
  8. concentrationconcentrated in vacuo (less than 30° C.)

Sources & evidence

ORD record
ord-fdbb98a46aae4416b1b6d133e5d716f5
Source dataset
uspto-grants-1990_09
Patent number
US04959293

Reaction notes

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