Ammonia → HCID 67195280, compound

HRID 877857Notes

Reaction equation

HRID 877857 reaction equation
C(Cl)(=O)C(Cl)=O.[CH:7]1([N:13]([CH:23]2[CH2:28][CH2:27][CH2:26][CH2:25][CH2:24]2)[C:14]([NH:16][N:17]2[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]2)=O)[CH2:12][CH2:11][CH2:10][CH2:9][CH2:8]1.[NH3:29]>C(OCC)C.C1COCC1>[CH:7]1([N:13]([CH:23]2[CH2:28][CH2:27][CH2:26][CH2:25][CH2:24]2)[C:14]([NH2:29])=[N:16][N:17]2[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]2)[CH2:12][CH2:11][CH2:10][CH2:9][CH2:8]1

Participants

6

Reactant 3

HCID 222AmmoniaHCID 65578Oxalyl chlorideHCID 67197281HCID 67197281, compound

Product 1

HCID 67195280HCID 67195280, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

A solution of dicyclohexylamine (4.0 mL, 20 mmol) and triethylamine (6 mL, 43 mmol) in diethyl ether (63 mL) was added dropwise to a stirred solution of triphosgene (2.0 g, 6.7 mmol) in diethyl ether (30 mL) at room temperature. The reaction mixture was stirred overnight under refluxing conditions. Then, a solution of piperidine (1.9 mL, 19 mmol) and triethylamine (5.8 mL, 42 mmol) in diethyl ether (37 mL) was added. The reaction mixture was stirred overnight at reflux temperature. The reaction mixture was filtered and the filtrate was evaporated to dryness, yielding N,N-dicyclohexylpiperidylurea as a yellow oil. Yield: 2.0 g (35%). Oxalyl chloride (1.0 mL, 12 mmol) was added to a stirred solution of the urea (2.0 g, 6.9 mmol) in diethyl ether (30 mL). The reaction mixture was evaporated to dryness after stirring at reflux temperature for 5 h. Ammonia (3 mL, 21 mmol, 7 M solution in methanol) was added to a solution of the resulting solid in diethyl ether (50 mL) and THF (5 mL). The reaction mixture was heated to reflux overnight and evaporated to dryness. The product mixture was treated with aqueous sodium hydroxide solution. The organic layer was extracted with diethyl ether and dried over sodium sulfate. Filtration and evaporation to dryness yielded the desired guanidine as a yellow solid. Yield: 1.76 g (87%). 1H NMR (CDCl3, 300 MHz): δ 1.18-1.89 (m 20 H), 3.03 (m, 6 H) ppm. 13C NMR (CDCl3, 75 MHz): δ 25.2, 26.1, 26.2, 32.4, 49.0, 57.8, 165.2 ppm.

Workup

  1. customThe reaction mixture was evaporated to dryness
  2. temperatureat reflux temperature for 5 h
  3. temperatureThe reaction mixture was heated
  4. temperatureto reflux overnight
  5. customevaporated to dryness
  6. additionThe product mixture was treated with aqueous sodium hydroxide solution
  7. extractionThe organic layer was extracted with diethyl ether
  8. dry with materialdried over sodium sulfate
  9. filtrationFiltration and evaporation to dryness

Sources & evidence

ORD record
ord-1db1ce9d8b4f45abaf42b7f25514cb59
Source dataset
uspto-grants-2015_03
Patent number
US08987393B2

Reaction notes

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