Isophorone → Tridecan-4-one

HRID 2072274Notes

Reaction equation

HRID 2072274 reaction equation
[O:1]=[C:2]1[CH2:9][C:6]([CH3:8])(C)C[C:4]([CH3:10])=[CH:3]1.[CH:11]12C[CH:14]([CH2:15][CH2:16]1)[CH:13]=[CH:12]2>ClCCl>[CH3:8][CH2:6][CH2:9][C:2](=[O:1])[CH2:3][CH2:4][CH2:10][CH2:15][CH2:16][CH2:11][CH2:12][CH2:13][CH3:14]

Participants

4

Reactant 2

HCID 6544IsophoroneHCID 103522-Norbornene

Product 1

HCID 98673Tridecan-4-one

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a Pyrex photoreactor equipped with a quartz immersion well and nitrogen bubbler was added, under nitrogen, 103.6 g. (0.75 mol.) of isophorone and 400 g. (4.25 mol) of freshly distilled bicyclo [2.2.1] hept-2-ene. The vessel was filled to its internal volume of 1200 ml. with dichloromethane. The solution was bubbled with nitrogen for 1 hour and irradiated through a Pyrex filter for 18.5 hours with an Hanovia 450 watt medium pressure mercury arc. After the lamp was turned off, the solution was concentrated in vacuo to obtain an oil which was distilled through a 90 cm. Vigreux-column to yield 143.6 g. (0.62 mol., 82%) of the desired product having b.p. 90°-94° C./0.5 mm.Hg. Glpc showed the product to be a 1:1 mixture of two main isomers (180 cm. × 0.3 cm. 1% OV-225 on Chrom G, 150° C. initially for 3 min. and then programmed 10° C./min. to 250° C.) IR: 1692 cm-1NMR: (CCl4) singlets at 1.35δ, 1.10δ, 1.00δ, 0.92δ, 0.87δ with the singlet at 1.00δ having an integral area of 6H while the others integrated to 3H. The rest of the NMR spectrum was a set of complicated multiplets.

Workup

  1. additionnitrogen bubbler was added, under nitrogen
  2. additionThe vessel was filled to its internal volume of 1200 ml
  3. customThe solution was bubbled with nitrogen for 1 hour
  4. customirradiated through a Pyrex
  5. filtrationfilter for 18.5 hours with an Hanovia 450 watt medium pressure mercury arc
  6. concentrationthe solution was concentrated in vacuo
  7. customto obtain an oil which
  8. distillationwas distilled through a 90 cm
  9. customVigreux-column to yield 143.6 g

Sources & evidence

ORD record
ord-a578e47d81f3413abae5b9b59dfcefdd
Source dataset
uspto-grants-1977_09
Patent number
US04051076

Reaction notes

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