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Hydrochloric Acid → tert-Butyl 3,5-bis(benzyloxy)-4-bromobenzoate

HRID 1177192
Notes
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Reaction equation

HRID 1177192 reaction equation
[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([CH:15]=[C:16]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C:17]=1[Br:18])[C:12]([OH:14])=[O:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1N=CN(C(N2C=NC=C2)=O)C=1.[CH3:39][C:40](O)([CH3:42])[CH3:41].C1CCN2C(=NCCC2)CC1.Cl>CN(C=O)C>[C:40]([O:13][C:12](=[O:14])[C:11]1[CH:10]=[C:9]([O:8][CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)[C:17]([Br:18])=[C:16]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[CH:15]=1)([CH3:42])([CH3:41])[CH3:39]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 6386tert-ButanolHCID 682631,1'-CarbonyldiimidazoleHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 100247103,5-Bis(benzyloxy)-4-bromobenzoic acid

Product 1

HCID 10389923tert-Butyl 3,5-bis(benzyloxy)-4-bromobenzoate
Yield 95%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
40 °C

Procedure

To a stirred solution of 3,5-bis-benzyloxy-4-bromo-benzoic acid (200b) (153 g, 0.37 mol) in DMF (1 L) was added CDI (90 g, 0.56 mol) in several portions. The solution was stirred at 40° C. for 1 hr. t-BuOH (55 g, 0.74 mol) was added to the mixture and then followed by the drop wise addition of DBU (56.3 g, 0.37 mol). The resulting solution was stirred at 40° C. for 2 days. TLC (EtOAc/petroleum ether=1/10) showed that the reaction was complete. The mixture was cooled to room temperature and poured into ice water (1 L). The mixture was acidified to pH 5 with conc. HCl and stirred for 1 hr. The formed solid was filtered and washed with water, then dried in vacuo to give the title compound (165 g, 86% yield) as a brown solid. 1H NMR (400 MHz, CDCl3): δ 7.57-7.25 (m, 12H), 5.21 (s, 4H), 1.58 (s, 9H).

Workup

  1. stirringThe resulting solution was stirred at 40° C. for 2 days
  2. temperatureThe mixture was cooled to room temperature
  3. stirringstirred for 1 hr
  4. filtrationThe formed solid was filtered
  5. washwashed with water
  6. customdried in vacuo

Sources & evidence

ORD record
ord-a08f849efc774ef9a24fac6a9b34f6b1
Source dataset
uspto-grants-2010_11
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07842713B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes