Diphosgene → Methyl trans-4-cyanocyclohexanecarboxylate

HRID 1691901Notes

Reaction equation

HRID 1691901 reaction equation
[CH3:1][O:2][C:3]([CH:5]1[CH2:10][CH2:9][CH:8]([C:11](=O)[NH2:12])[CH2:7][CH2:6]1)=[O:4].O=C(Cl)OC(Cl)(Cl)Cl>P(OC)(OC)(OC)=O.C(OCC)(=O)C>[CH3:1][O:2][C:3]([CH:5]1[CH2:10][CH2:9][CH:8]([C:11]#[N:12])[CH2:7][CH2:6]1)=[O:4]

Participants

5

Reactant 2

HCID 10426DiphosgeneHCID 15105949Methyl 4-carbamoylcyclohexanecarboxylate

Product 1

HCID 11389613Methyl trans-4-cyanocyclohexanecarboxylateYield 36%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 10541Trimethyl PhosphateSolvent

Procedure

To a mixture of 4-carbamoyl-cyclohexanecarboxylic acid methyl ester (2.14 g, 11.6 mmol) in trimethyl phosphate (14 mL) cooled in an ice bath was dripped in diphosgene (2.24 g 11.6 mmol) and the reaction was allowed to warm to room temperature over 2 hr. The material was diluted with ethyl acetate (200 mL) and washed with an aqueous sodium bicarbonate (saturated, 200 mL) and brine (200 mL), dried over sodium sulfate, and concentrated as a clear oil. The oil was triturated with hexanes to give 4-cyano-cyclohexanecarboxylic acid methyl ester (687 mg 36%) as a clear oil. LCMS calcd for C9H13NO2 (m/e) 167, obsd 168 (M+H).

Workup

  1. temperaturecooled in an ice bath
  2. washwashed with an aqueous sodium bicarbonate (saturated, 200 mL) and brine (200 mL)
  3. dry with materialdried over sodium sulfate
  4. concentrationconcentrated as a clear oil
  5. customThe oil was triturated with hexanes

Sources & evidence

ORD record
ord-68619a4bcc8748559faed798080d7503
Source dataset
uspto-grants-2012_04
Patent number
US08153644B2

Reaction notes

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