Ammonia → HCID 67194825, compound

HRID 877863Notes

Reaction equation

HRID 877863 reaction equation
C(Cl)(=O)C(Cl)=O.[CH3:7][N:8]([CH2:24][CH:25]([CH3:27])[CH3:26])[C:9]([N:11]([CH:18]1[CH2:23][CH2:22][CH2:21][CH2:20][CH2:19]1)[CH:12]1[CH2:17][CH2:16][CH2:15][CH2:14][CH2:13]1)=O.[NH3:28].CO>C1COCC1>[CH3:7][N:8]([CH2:24][CH:25]([CH3:27])[CH3:26])[C:9]([N:11]([CH:18]1[CH2:23][CH2:22][CH2:21][CH2:20][CH2:19]1)[CH:12]1[CH2:17][CH2:16][CH2:15][CH2:14][CH2:13]1)=[NH:28]

Participants

6

Reactant 4

HCID 222AmmoniaHCID 887MethanolHCID 65578Oxalyl chlorideHCID 67194883HCID 67194883, compound

Product 1

HCID 67194825HCID 67194825, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of dicyclohexylamine (3.6 mL, 18 mmol) and triethylamine (5.6 mL, 40 mmol) in THF (64 mL) was added dropwise to a stirred solution of triphosgene (1.98 g, 6.7 mmol) in THF (35 mL) at room temperature. The reaction mixture was stirred overnight. Then, a solution of N-methylisobutylamine (2.2 mL, 18 mmol) and triethylamine (5.5 mL, 40 mmol) in THF (35 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-methyl-N-isobutyl-N′,N′-dicyclohexylurea as a dark yellow oil. Yield: 4.8 g (90%). Oxalyl chloride (8 mL, 16 mmol, 2 M solution in dichloromethane) was added to a stirred solution of the urea (4.8 g, 16 mmol) in THF (65 mL). The reaction mixture was heated to reflux overnight and evaporated to dryness. Ammonia in methanol (7 mL, 49 mmol, 7 M solution in methanol) was added to a suspension of the formed solid in THF. The reaction mixture was heated to reflux overnight and evaporated to dryness. The product was neutralized and purified by treatment with aqueous sodium hydroxide solution. The organic layer was extracted with diethyl ether and dried over magnesium sulfate. Evaporation to dryness yielded the desired guanidine as a brown oil. Yield: 2.95 g (75%). 1H NMR (CDCl3, 300 MHz): δ 0.80 (d, 6 H), 1.20 (d, 12 H), 1.8 (sept, 1 H), 2.7 (s, 3 H), 2.83 (d, 2 H), 3.52 (sept, 1 H) ppm. 13C NMR (CDCl3, 75 MHz): δ 19.1, 20.7, 25.6, 36.8, 46.4, 57.2, 164.7 ppm.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux overnight
  3. customevaporated to dryness
  4. temperatureThe reaction mixture was heated
  5. temperatureto reflux overnight
  6. customevaporated to dryness
  7. custompurified by treatment with aqueous sodium hydroxide solution
  8. extractionThe organic layer was extracted with diethyl ether
  9. dry with materialdried over magnesium sulfate
  10. customEvaporation to dryness

Sources & evidence

ORD record
ord-311ce2a7199f4ad789f1ab6d005690ab
Source dataset
uspto-grants-2015_03
Patent number
US08987393B2

Reaction notes

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