Formic Acid → HCID 14255315, compound

HRID 1755655Notes

Reaction equation

HRID 1755655 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:15]=[CH:16][CH:17]=1)[O:5][CH2:6][C:7]1[CH:14]=[CH:13][CH:12]=[CH:11][C:8]=1[C:9]#N.C(O)=[O:19]>[Ni]>[Cl:1][C:2]1[CH:3]=[C:4]([CH:15]=[CH:16][CH:17]=1)[O:5][CH2:6][C:7]1[CH:14]=[CH:13][CH:12]=[CH:11][C:8]=1[CH:9]=[O:19]

Participants

4

Reactant 2

HCID 284Formic AcidHCID 142553142-[(3-Chlorophenoxy)methyl]benzonitrile

Product 1

HCID 14255315HCID 14255315, compound

Reagents, catalysts & solvents 1

HCID 935NickelCatalyst2×

Conditions

Temperature
150 °C

Procedure

Raney nickel alloy (9.72 g) was added to a solution of part of the crude (2-(3-chlorophenoxymethyl)benzonitrile (9.72 g) in 75% formic acid (150 ml). The resulting mixture was heated at 150° C. for about 5 hours, further Raney nickel alloy (3 g) was added, and heating at 150° C. was continued for a further 17 hours. The mixture was filtered and the solid was washed with a little methanol. The combined filtrate and washings were diluted with water and extracted with ether. The extracts was washed successively with water, aqueous potassium carbonate and brine, then dried and concentrated to give 2-(3-chlorophenoxymethyl)benzaldehyde (5.80 g) as a yellow-brown oil, 1H NMR delta 5.51 (2H, s), 10.18 (1H, s) ppm. A mixture of this crude benzaldehyde, methyl(methylthiomethyl)sulphoxide (1.73 g) and Triton B [(40 weight % solution of benzyltrimethylammonium hydroxide in methanol) 1.21 ml] in THF (6 ml) was heated at 110° C. for 3 hours. Further Triton B (2 ml) was added and the mixture was heated for a further 4 hours at 110° C. Further Triton B (2 ml) and methyl (methylthiomethyl)sulphoxide (1.5 ml ) were then added and the mixture was heated for a further 6 hours at 110° C. After cooling, the mixture was poured into water and extracted with ether. The extracts were washed with water and brine, dried, concentrated and chromatographed using ether as eluant to give a single stereoisomer of the sulphoxide (A) [1.10 g, 7% yield from 2-(bromomethyl)benzonitrile] as a viscous oil, 1H NMR delta 2.18 (3H, s), 2.74 (3H, s), 5.04 and 5.12 (each 1H, d J 12 Hz), 7.85 (1H, s) ppm. ##STR53##

Workup

  1. temperatureheating at 150° C.
  2. filtrationThe mixture was filtered
  3. washthe solid was washed with a little methanol
  4. additionThe combined filtrate and washings were diluted with water
  5. extractionextracted with ether
  6. washThe extracts was washed successively with water, aqueous potassium carbonate and brine
  7. customdried
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-a3b0dc600b714e2ca47db09faa7b4a72
Source dataset
uspto-grants-1995_08
Patent number
US05438059

Reaction notes

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