Ammonia → HCID 67195176, compound

HRID 877861Notes

Reaction equation

HRID 877861 reaction equation
C(Cl)(=O)C(Cl)=O.ClCCl.[CH:10]1([N:16]([CH:32]2[CH2:37][CH2:36][CH2:35][CH2:34][CH2:33]2)[C:17](=O)[N:18]([CH:25]2[CH2:30][CH2:29][CH2:28][CH2:27][CH2:26]2)[CH:19]2[CH2:24][CH2:23][CH2:22][CH2:21][CH2:20]2)[CH2:15][CH2:14][CH2:13][CH2:12][CH2:11]1.[NH3:38].CO>C1COCC1>[CH:10]1([N:16]([CH:32]2[CH2:37][CH2:36][CH2:35][CH2:34][CH2:33]2)[C:17]([N:18]([CH:25]2[CH2:30][CH2:29][CH2:28][CH2:27][CH2:26]2)[CH:19]2[CH2:24][CH2:23][CH2:22][CH2:21][CH2:20]2)=[NH:38])[CH2:15][CH2:14][CH2:13][CH2:12][CH2:11]1

Participants

7

Reactant 5

HCID 222AmmoniaHCID 887MethanolHCID 6344DichloromethaneHCID 65578Oxalyl chlorideHCID 12887429HCID 12887429, compound

Product 1

HCID 67195176HCID 67195176, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of dicyclohexylamine (3.9 mL, 19 mmol) and triethylamine (6 mL, 43 mmol) in THF (64 mL) was added dropwise to a stirred solution of triphosgene (1.99 g, 6.7 mmol) in THF (35 mL) at room temperature. The reaction mixture was stirred overnight. Then, a solution of dicyclohexylamine (3.9 mL, 18 mmol) and triethylamine (6 mL, 43 mmol) in THF (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 tetracyclohexylurea as a yellow solid. Yield: 4.5 g (65%). A solution of oxalyl chloride in dichloromethane (1.1 mL, 13 mmol) was added to a stirred solution of the urea (4.5 g, 11 mmol) in THF (50 mL). The reaction mixture was evaporated to dryness after overnight heating to reflux. A solution of ammonia in methanol (5 mL, 35 mmol, 7 M) was added to a solution of the formed solid in THF (40 mL). The reaction mixture was heated to reflux overnight and evaporated to dryness. The product was neutralized and treated with aqueous sodium hydroxide solution. The organic layer was extracted with diethyl ether and dried over magnesium sulfate. Crystallization from hexanes yielded the desired guanidine as a brown solid. Yield: 2.9 g (64%). 13C NMR (CDCl3, 75 MHz): δ 25.4, 26.2, 31.8, 58.0, 156.2 ppm.

Workup

  1. customThe reaction mixture was evaporated to dryness after overnight
  2. temperatureheating to reflux
  3. temperatureThe reaction mixture was heated
  4. temperatureto reflux overnight
  5. customevaporated to dryness
  6. additiontreated with aqueous sodium hydroxide solution
  7. extractionThe organic layer was extracted with diethyl ether
  8. dry with materialdried over magnesium sulfate
  9. customCrystallization from hexanes

Sources & evidence

ORD record
ord-2c9abf87479043718ec4dc45d65474b9
Source dataset
uspto-grants-2015_03
Patent number
US08987393B2

Reaction notes

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