Methanol → (4-(Pyridin-2-yloxy)benzene)-acetohydroximoyl chloride

HRID 1694206Notes

Reaction equation

HRID 1694206 reaction equation
CO.[N+:3]([CH2:6][CH2:7][C:8]1[CH:20]=[CH:19][C:11]([O:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][N:14]=2)=[CH:10][CH:9]=1)([O-])=[O:4].C[O-].[Li+].O1CCCC1.C(Cl)[Cl:30]>[Ti](Cl)(Cl)(Cl)Cl.C(OCC)(=O)C>[C:6]([Cl:30])(=[N:3][OH:4])[CH3:7].[N:14]1[CH:15]=[CH:16][CH:17]=[CH:18][C:13]=1[O:12][C:11]1[CH:10]=[CH:9][CH:8]=[CH:20][CH:19]=1

Participants

8

Reactant 5

HCID 887MethanolHCID 6344DichloromethaneHCID 8028TetrahydrofuranHCID 4177230Lithium methanolateHCID 592552412-(4-(2-Nitro-ethyl)-phenoxy)-pyridine

Product 1

HCID 86612460(4-(Pyridin-2-yloxy)benzene)-acetohydroximoyl chlorideYield 98%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-76 °C

Procedure

To a methanol solution (30 mL) of 2-(4-(2-nitro-ethyl)-phenoxy)-pyridine (2.0 g, 8.2 mmol) described in Manufacturing Example 209-1-3 was added lithium methoxide (470 mg, 12 mmol), and this mixture was concentrated under a reduced pressure. Toluene was added to the residue, and the solvent was evaporated under a reduced pressure. To a solution of this residue in methylene chloride (40 mL) and tetrahydrofuran (20 mL) was added titanium (IV) tetrachloride (2.3 mL, 21 mmol) while stirring at −76° C. This suspension was stirred for 15 minutes at 0° C., and then for another 20 minutes at room temperature. The mixture was poured into ice water and stirred for 30 minutes. Ethyl acetate was added, and the organic layer was separated, washed with aqueous sodium chloride (one time), dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under a reduced pressure to obtain the title compound (2.1 g, 98%).

Workup

  1. concentrationthis mixture was concentrated under a reduced pressure
  2. additionToluene was added to the residue
  3. customthe solvent was evaporated under a reduced pressure
  4. stirringThis suspension was stirred for 15 minutes at 0° C.
  5. stirringstirred for 30 minutes
  6. customthe organic layer was separated
  7. washwashed with aqueous sodium chloride (one time)
  8. dry with materialdried over anhydrous magnesium sulfate
  9. filtrationfiltered
  10. concentrationThe filtrate was concentrated under a reduced pressure

Sources & evidence

ORD record
ord-5e3c228bd4454730bba4ec63bba5bb3f
Source dataset
uspto-grants-2012_04
Patent number
US08158657B2

Reaction notes

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