Methanol → (6-Benzyl-pyridin-3-yl)-acetohydroximoyl chloride

HRID 1691365Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1691365
[CH2:1]([C:8]1[CH:13]=[CH:12][C:11]([CH2:14][CH2:15][N+:16]([O-:18])=O)=[CH:10][N:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CO.C[O-].[Li+].C(Cl)[Cl:25]>O1CCCC1.[Ti](Cl)(Cl)(Cl)Cl>[CH2:1]([C:8]1[N:9]=[CH:10][C:11]([CH2:14][C:15]([Cl:25])=[N:16][OH:18])=[CH:12][CH:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Komponenten

7

Edukt 4

HCID 887MethanolHCID 6344DichloromethaneHCID 4177230Lithium methanolateHCID 592551352-Benzyl-5-(2-nitro-ethyl)-pyridine

Produkt 1

HCID 72262889(6-Benzyl-pyridin-3-yl)-acetohydroximoyl chlorideAusbeute 63 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24193Titanium TetrachlorideKatalysatorHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

To 2-benzyl-5-(2-nitro-ethyl)-pyridine (260 mg, 1.1 mmol) described in Manufacturing Example 210-1-6 and methanol (5 mL) was added lithium methoxide (81 mg, 2.1 mmol), which was concentrated under a reduced pressure. Titanium(IV) tetrachloride (0.38 mL, 3.4 mmol) was added dropwise at −76° C. to a suspension of the residue in methylene chloride (5 mL) and tetrahydrofuran (2.5 mL), which was stirred for 20 minutes at room temperature. This reaction solution was added to ice water and extracted with ethyl acetate. The aqueous layer was extracted with ethyl acetate again (four times). The organic layers were combined, washed with aqueous sodium chloride (one time), dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under a reduced pressure, and tetrahydrofuran was added to the residue. The insolubles thus produced were filtered out. The filtrate was concentrated under a reduced pressure to obtain the title compound (180 mg, 63%).

Aufarbeitung

  1. concentrationwas concentrated under a reduced pressure
  2. extractionextracted with ethyl acetate
  3. extractionThe aqueous layer was extracted with ethyl acetate again (four times)
  4. washwashed with aqueous sodium chloride (one time)
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated under a reduced pressure, and tetrahydrofuran
  8. additionwas added to the residue
  9. customThe insolubles thus produced
  10. filtrationwere filtered out
  11. concentrationThe filtrate was concentrated under a reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-b1f73cc1ebad46a0babb8838ca0e5573
Quelldatensatz
uspto-grants-2012_04
Patentnummer
US08153662B2

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