Acetic Acid → N-{4-[4-(2-tert-Butoxycarbonylaminoethylamino)phenyl]butyl)carbamic acid benzyl ester

HRID 254386Notes

Reaction equation

HRID 254386 reaction equation
[C:1]([O:5][C:6]([NH:8][CH2:9][CH:10]=O)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH2:12]([O:19][C:20](=[O:33])[NH:21][CH2:22][CH2:23][CH2:24][CH2:25][C:26]1[CH:31]=[CH:30][C:29]([NH2:32])=[CH:28][CH:27]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C(O)(=O)C.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+].Cl>ClCCCl.O>[CH2:12]([O:19][C:20](=[O:33])[NH:21][CH2:22][CH2:23][CH2:24][CH2:25][C:26]1[CH:31]=[CH:30][C:29]([NH:32][CH2:10][CH2:9][NH:8][C:6]([O:5][C:1]([CH3:2])([CH3:3])[CH3:4])=[O:7])=[CH:28][CH:27]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

8

Reactant 5

HCID 176Acetic AcidHCID 313Hydrochloric AcidHCID 4247255tert-butyl N-(2-oxoethyl)carbamateHCID 5049666Sodium triacetoxyborohydrideHCID 58664834[4-(4-Aminophenyl)butyl]carbamic acid benzyl ester

Product 1

HCID 58664847N-{4-[4-(2-tert-Butoxycarbonylaminoethylamino)phenyl]butyl)carbamic acid benzyl esterYield 47%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolvent2×HCID 962WaterSolvent

Procedure

A solution of N-tert-butoxycarbonylaminoacetaldehyde (0.28 g, 1.76 mmol) in 1,2-dichloroethane (DCE, 5 mL) was added to a solution of [4-(4-aminophenyl)butyl]carbamic acid benzyl ester (0.48 g, 1.6 mmol) in DCE (10 mL) and acetic acid (0.108 mL, 1.6 mmol). The mixture was stirred at room temperature for 20 min. NaB(OAc)3H (0.48 g, 2.26 mmol) was then added into the mixture which was further stirred at room temperature overnight. Water (10 mL) was added and the mixture was acidified to pH 7 by 10% aqueous HCl. The organic fraction was isolated and dried over sodium sulfate. The solvent was removed under reduced pressure and the residue was purified by Flash™ (BIOTAGE, Inc) (90 g silica gel cartridge 40M, ethyl acetate/hexane, 1:2, v/v) to afford the protected diamine 600 (0.33 g, 47%) as a white powder. 1H NMR (300 MHz, CDCl3) δ 1.45 (s, 9H), 1.54 (m, 2H), 2.51 (m, 2), 3.18 (m, 4H), 3.36 (m, 2H), 3.89 (br s, 1H), 4.69 (br s, 1H), 4.78 (br s, 1H), 5.51 (s, 2H), 6.54 (d, 2), 6.96 (d, 2H), 7.33 (m, 5H). m/z (ESI) 442 [C25H35N3O4+H]+.

Workup

  1. stirringwas further stirred at room temperature overnight
  2. customThe organic fraction was isolated
  3. dry with materialdried over sodium sulfate
  4. customThe solvent was removed under reduced pressure
  5. customthe residue was purified by Flash™ (BIOTAGE, Inc) (90 g silica gel cartridge 40M, ethyl acetate/hexane, 1:2

Sources & evidence

ORD record
ord-8a922a51a53f4b6194ee3ebdb72adaba
Source dataset
uspto-grants-2011_01
Patent number
US07875619B2

Reaction notes

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