Guanidine Hydrochloride → 10065-79-9

HRID 844480Notes

Reaction equation

HRID 844480 reaction equation
Cl.[NH2:2][C:3]([NH2:5])=[NH:4].[OH-:6].[Na+].[CH2:8]([O:15][C:16](Cl)=[O:17])[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1>O.ClCCl>[C:16]([NH:4][C:3]([NH:5][C:16]([O:15][CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=[O:6])=[NH:2])([O:15][CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=[O:17]

Participants

6

Reactant 3

HCID 5742Guanidine HydrochlorideHCID 10387Benzyl chloroformateHCID 14798Sodium Hydroxide

Product 1

HCID 13783255110065-79-9Yield 75.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

Dichloromethane (80 ml) is added to a solution of guanidine hydrochloride (3.82 g, 40 mmol) and sodium hydroxide (8 g, 0.2 mol) in water (40 ml) and the resulting mixture is cooled to 0° C. Benzyloxycarbonyl chloride (17.1 ml, 120 mmol) is added dropwise with vigorous stirring over a period of 45 min. After the addition is completed, stirring is continued for 20 h at 0° C. The mixture is diluted with dichloromethane (100 ml), the layers are separated and the aqueous layer is extracted with dichloromethane (100 ml). The extracts are combined, washed with water and dried with magnesium sulfate. After filtering and removal of the solvent under reduced pressure the crude product is recrystallized from methanol. N-,N′-Di-Cbz-guanidine (9.85 g, 75%) is obtained as colorless crystals: mp: 149-150° C.; 1H NMR (360 MHz, DMSO-d6) δ 10.88 (br s, 1H), 8.67 (br s, 2H), 7.40-7.25 (m, 10H), 5.10 (s, 4H); Anal. Calc. for C, 62.38%; H, 5.23%;.N, 12.84%. Found: C, 62.26%; H, 5.01%;.N, 12.79%.

Workup

  1. additionAfter the addition
  2. stirringstirring
  3. waitis continued for 20 h at 0° C
  4. customthe layers are separated
  5. extractionthe aqueous layer is extracted with dichloromethane (100 ml)
  6. washwashed with water
  7. dry with materialdried with magnesium sulfate
  8. filtrationAfter filtering
  9. customremoval of the solvent under reduced pressure the crude product
  10. customis recrystallized from methanol

Sources & evidence

ORD record
ord-720db9a5a44d4656855aa38d2ba4cd25
Source dataset
uspto-grants-2002_04
Patent number
US06380358B1

Reaction notes

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