Acetic Acid → Benzyl 14-azido-3-methyl-6,9,12-trioxa-3-azatetradecyl(methyl)carbamate

HRID 1408256Notes

Reaction equation

HRID 1408256 reaction equation
C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].[CH3:15][N:16]([CH2:27][CH:28]=O)[C:17](=[O:26])[O:18][CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.[N:30]([CH2:33][CH2:34][O:35][CH2:36][CH2:37][O:38][CH2:39][CH2:40][O:41][CH2:42][CH2:43][NH:44][CH3:45])=[N+:31]=[N-:32].C(O)(=O)C>C1COCC1.C(OCC)(=O)C>[N:30]([CH2:33][CH2:34][O:35][CH2:36][CH2:37][O:38][CH2:39][CH2:40][O:41][CH2:42][CH2:43][N:44]([CH3:45])[CH2:28][CH2:27][N:16]([CH3:15])[C:17](=[O:26])[O:18][CH2:19][C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1)=[N+:31]=[N-:32]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 5049666Sodium triacetoxyborohydrideHCID 12010768Benzyl N-methyl-N-(2-oxoethyl)carbamateHCID 59887697Methylamino-PEG3-azide

Product 1

HCID 86706004Benzyl 14-azido-3-methyl-6,9,12-trioxa-3-azatetradecyl(methyl)carbamateYield 58.4%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

Sodium triacetoxyborohydride (3.55 g, 16.8 mmol) was added portionwise at room temperature to benzyl methyl(2-oxoethyl)carbamate (2.68 g, 12.9 mmol), 2-(2-(2-(2-azidoethoxy)ethoxy)ethoxy)-N-methylethanamine 222c (3.00 g, 12.9 mmol), and acetic acid (2 equiv.) in THF (20 mL). The mixture was stirred for 2 hours, diluted with ethyl acetate, washed with saturated aqueous sodium bicarbonate and brine, dried (Mg2SO4) and evaporated. The residue was purified by Combiflash purification system (ethyl acetate/dichloromethane) to give product as an oil (3.19 g, 58%); MS (ES, m/z): 424 [M+H]+.

Workup

  1. washwashed with saturated aqueous sodium bicarbonate and brine
  2. dry with materialdried (Mg2SO4)
  3. customevaporated
  4. customThe residue was purified by Combiflash purification system (ethyl acetate/dichloromethane)

Sources & evidence

ORD record
ord-a3b77ef686624bf8a020ebc887bcfac3
Source dataset
uspto-grants-2014_12
Patent number
US08916569B2

Reaction notes

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