Hydrochloric Acid → (Boc)2NN(Boc)CH2CONHCH2CH2N3

HRID 884348Notes

Reaction equation

HRID 884348 reaction equation
C([NH:8][CH2:9][CH2:10][N:11]=[N+:12]=[N-:13])(OC(C)(C)C)=O.[N:14]([N:29]([CH2:37][C:38]([OH:40])=O)[C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16].C1CN([P+](O[N:58]2[N:66]=[N:65][C:60]3[CH:61]=CC=CC2=3)(N2CCCC2)N2CCCC2)CC1.F[P-](F)(F)(F)(F)F.CC[N:76](CC)CC.[ClH:81]>O1CCOCC1.C(Cl)Cl.CN(C=O)C>[NH2:8][CH2:9][CH2:10][N:11]=[N+:12]=[N-:13].[ClH:81].[N:14]([N:29]([CH2:37][C:38]([NH:76][CH2:61][CH2:60][N:65]=[N+:66]=[N-:58])=[O:40])[C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 2724699PyBOPHCID 9930318Tri-Boc-hydrazinoacetic acidHCID 22323692tert-Butyl (2-azidoethyl)carbamate

Product 2

HCID 135382832-Azidoethan-1-amine hydrochlorideHCID 131729880(Boc)2NN(Boc)CH2CONHCH2CH2N3Yield 95%

Reagents, catalysts & solvents 2

HCID 312751,4-DioxaneSolventHCID 22350042dichloromethane N,N-dimethylformamideSolvent

Procedure

HCl.H2NCH2CH2N3 (4) was synthesized by dissolving azide 3 (2.11 g, 11.33 mmol) in 4 N HCl in dioxane (100 mL) and stirring at room temperature for 1 h. The solvent was removed under reduced pressure to give a dirty white powder. (Boc)2NN(Boc)CH2CO2H (4.42 g, 11.33 mmol) was then added, and the mixture was dissolved in methylene chloride/DMF (70:45 mL). The mixture was cooled to 0° C., and PyBOP (5.9 g, 11.33 mmol) and Et3N (3.2 mL, 22.66 mmol) were added. The reaction mixture was allowed to warm to room temperature and stirred under Ar(g) for 21 h. The solvent was removed under reduced pressure, and the residue was purified by flash chromatography (silica gel, 50% v/v ethyl acetate in hexanes) to give (Boc)2NN(Boc)CH2CONHCH2CH2N3 as a colorless viscous oil (4.9 g, 95%). HRMS (ESI) [M+Na]+ calcd for C19H34N6O7Na, 481.2387; found, 481.2389; 1H NMR (400 MHz, CDCl3, 2 rotamers) δ 8.51 and 8.27 (bs, 1H), 4.06 and 3.99 (s, 2H), 3.49-3.40 (m, 4H), 1.56-1.44 (m, 27H); 13C NMR (100 MHz, CDCl3, 2 rotamers) δ 169.5, 169.2, 154.0, 153.5, 151.4, 151.2, 85.2, 85.1, 83.5, 82.8, 56.5, 54.8, 50.6, 38.9, 34.1, 29.9, 28.2, 28.1.

Workup

  1. customThe solvent was removed under reduced pressure
  2. customto give a dirty white powder
  3. temperatureThe mixture was cooled to 0° C.
  4. temperatureto warm to room temperature
  5. customThe solvent was removed under reduced pressure
  6. customthe residue was purified by flash chromatography (silica gel, 50% v/v ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-acfc7bd849de4fa48f801bc4c8f5fe5c
Source dataset
uspto-grants-2012_08
Patent number
US08242058B2

Reaction notes

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