Hexamethylenetetramine → 3-Formyl-2-hydroxybenzonitrile

HRID 401176Notes

Reaction equation

HRID 401176 reaction equation
[OH:1][C:2]1[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=1[C:4]#[N:5].C1N2CN3CN(C2)CN1C3.C[CH2:21][O:22]C(C)=O>C(O)(=O)C>[CH:21]([C:7]1[CH:8]=[CH:9][C:2]([OH:1])=[C:3]([CH:6]=1)[C:4]#[N:5])=[O:22].[CH:21]([C:9]1[C:2]([OH:1])=[C:3]([CH:6]=[CH:7][CH:8]=1)[C:4]#[N:5])=[O:22]

Participants

6

Reactant 3

HCID 4101HexamethylenetetramineHCID 8857Ethyl AcetateHCID 119072-Hydroxybenzonitrile

Product 2

HCID 205546503-Formyl-2-hydroxybenzonitrileYield 19%HCID 221125485-Formyl-2-hydroxybenzonitrileYield 9%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
120 °C

Procedure

To a solution of 2-hydroxybenzonitrile (4.70 g, 41.6 mmol) in acetic acid (40 mL) was added hexamethylenetetraamine (8.7 g, 62.4 mmol) and the mixture was heated to 120° C. for 2 h. The mixture was cooled to room temperature, followed by a standard aqueous/EtOAc workup and purified by silica gel column chromatography (PE:EA=1:1) to afford 5-formyl-2-hydroxybenzonitrile (Intermediate 47a) as a white powder (540 mg, 9%) and 3-formyl-2-hydroxybenzonitrile (Intermediate 47b) as a white powder (1.17 g, 19%).

Workup

  1. temperatureThe mixture was cooled to room temperature
  2. custompurified by silica gel column chromatography (PE:EA=1:1)

Sources & evidence

ORD record
ord-5eaa78cf4ab94fd381a9aef920925190
Source dataset
uspto-grants-2014_06
Patent number
US08741915B2

Reaction notes

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