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Hydrochloric Acid → 5-Dibutylamino-2-methoxy-benzaldehyde

HRID 1989813
Notes
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Reaction equation

HRID 1989813 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([O:14][CH3:15])=[C:6]([CH:8]2[O:13]CCCO2)[CH:7]=1.[CH2:16]([NH:20][CH2:21][CH2:22][CH2:23][CH3:24])[CH2:17][CH2:18][CH3:19].CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.Cl.[OH-].[Na+]>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:16]([N:20]([CH2:21][CH2:22][CH2:23][CH3:24])[C:2]1[CH:3]=[CH:4][C:5]([O:14][CH3:15])=[C:6]([CH:7]=1)[CH:8]=[O:13])[CH2:17][CH2:18][CH3:19]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 8148DibutylamineHCID 14798Sodium HydroxideHCID 80271Tri-o-tolylphosphineHCID 143787592-(5-Bromo-2-methoxyphenyl)-1,3-dioxane

Product 1

HCID 858889065-Dibutylamino-2-methoxy-benzaldehydeYield 46%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
25 °C

Procedure

2-(5-Bromo-2-methoxy-phenyl)-[1,3]dioxane (40 mmol), di-n-butylamine (48 mmol), Pd2(dba)3 (0.2 mmol, 1 mol % Pd), P(o-tol)3 (0.6 mmol) and Na-t-OBu (68 mmol) was stirred in degassed toluene (60 mL) at 80° C. for 18 h. The darkbrown mixture was poured into icecold hydrochloric acid (1 M, 200 mL) and stirred vigorously for 2 hours at 25° C. The solution was cooled to 0° C. and pH was adjusted to 9 using 6M NaOH(aq) and extracted with Et2O (4×100 mL). The organic phase was dried (Na2SO4) and the solvent was removed under reduced pressure. The resulting crude oil purified by flash chromatography using EtOAc/n-heptane (1:4, v/v) as eluent. The product was isolated as yellow oil in 46% yield.

Workup

  1. temperatureThe solution was cooled to 0° C.
  2. extractionextracted with Et2O (4×100 mL)
  3. dry with materialThe organic phase was dried (Na2SO4)
  4. customthe solvent was removed under reduced pressure
  5. customThe resulting crude oil purified by flash chromatography
  6. customThe product was isolated as yellow oil in 46% yield

Sources & evidence

ORD record
ord-8261bab93a224a1980c3988478e40b97
Source dataset
uspto-grants-2010_01
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07642367B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes