tert-Butyl bromoacetate → HCID 15319065, compound

HRID 1523111Notes

Reaction equation

HRID 1523111 reaction equation
[CH2:1]([O:8][C:9]([N:11]1[CH2:22][CH2:21][NH:20][CH2:19][CH2:18][N:17]([C:23]([O:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)=[O:24])[CH2:16][CH2:15][NH:14][CH2:13][CH2:12]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Br[CH2:34][C:35]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])=[O:36]>CC#N>[CH2:1]([O:8][C:9]([N:11]1[CH2:12][CH2:13][N:14]([CH2:34][C:35]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])=[O:36])[CH2:15][CH2:16][N:17]([C:23]([O:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)=[O:24])[CH2:18][CH2:19][N:20]([CH2:34][C:35]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])=[O:36])[CH2:21][CH2:22]1)=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 79177tert-Butyl bromoacetateHCID 393883Dibenzyl 1,4,7,10-tetraazacyclododecane-1,7-dicarboxylate

Product 1

HCID 15319065HCID 15319065, compoundYield 92%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of compound (18) (6.84 g, 15.53 mmol) in dry MeCN (150 ml) were added N,N′-diisopropylethyl amine (13.52 ml, 10.03 g, 77.63 mmol) and tert-butyl bromoacetate (4.82 ml, 6.36 g, 32.61 mmol). The reaction mixture was slowly heated to 60° C., and stirred for 10 hours. The solvent was evaporated under reduced pressure, and the residue was dissolved in a Na2CO3 solution (100 ml). The aqueous layer was extracted with CH2Cl2 (3×100 ml), and the combined extract was washed with brine and dried over MgSO4 to obtain a concentrated white oil. The oil was recrystallized from Et2O to provide compound (19) as a white solid (9.55 g, 92% yield). 1H NMR (500 MHz, CDCl3): δ 7.26-7.19 (m, 10H), 5.04 (s, 4H), 3.34-3.05 (m, 12H), 2.9-2.6 (m, 8H), 1.35 (s, 18H); 13C NMR (125 MHz, CDCl3): δ 170.4, 156.3, 136.7, 128.3, 127.8, 127.7, 80.8, 66.8, 55.8, 54.2, 46.9, 46.5, 28.1; HRMS (FAB) calculated for C36H53N4O8: 669.3863 [(M+H)+], measured value: 669.3860 [(M+H)+].

Workup

  1. customThe solvent was evaporated under reduced pressure
  2. dissolutionthe residue was dissolved in a Na2CO3 solution (100 ml)
  3. extractionThe aqueous layer was extracted with CH2Cl2 (3×100 ml)
  4. extractionthe combined extract
  5. washwas washed with brine
  6. dry with materialdried over MgSO4
  7. customto obtain a concentrated white oil
  8. customThe oil was recrystallized from Et2O

Sources & evidence

ORD record
ord-e094cab9103f463aba23ed29c3b881c3
Source dataset
uspto-grants-2015_07
Patent number
US09079867B2

Reaction notes

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