Dichloromethane → 1(2H)-Biphenylenone, decahydro-3,3,4a-trimethyl-

HRID 2072273Notes

Reaction equation

HRID 2072273 reaction equation
[O:1]=[C:2]1[CH2:9][C:6]([CH3:8])([CH3:7])[CH2:5][C:4]([CH3:10])=[CH:3]1.[CH:11]1[CH2:16][CH2:15]C[CH2:13][CH:12]=1.Cl[CH2:18]Cl>>[CH3:10][C:4]1([CH3:18])[CH2:5][C:6]2([CH3:8])[CH:9]([CH:13]3[CH:7]2[CH2:15][CH2:16][CH2:11][CH2:12]3)[C:2](=[O:1])[CH2:3]1

Participants

4

Reactant 3

HCID 6344DichloromethaneHCID 6544IsophoroneHCID 8079Cyclohexene

Product 1

HCID 1126531(2H)-Biphenylenone, decahydro-3,3,4a-trimethyl-Yield 82%

Procedure

To a photoreactor fitted with a quartz immersion well and nitrogen bubbler was added, under nitrogen, 30.0 g. (0.217 mol.) of isophorone and 145 ml. of freshly distilled cyclohexene. Enough dichloromethane was added to fill the 825 ml. internal volume of the photoreactor. After the solution was bubbled with nitrogen for 1 hour, it was irradiated through a Corning 9700 glass filter for 71/4 hours with an Hanovia 450 watt medium pressure mercury arc. At the end of this period, the solution was concentrated in vacuo to yield an oil which was distilled through a short Vigreux-column. The product, which is a mixture of two major isomers in approximately a 3:1 ratio had b.p. 93°-106° C./0.2 mm.Hg. Yield 39.2 g. (0.178 mol., 82% yield). The two major isomers could be separated by distillation on a spinning band column. Isomer A: b.p. 85° C./0.1 mm.Hg. m.p. 76.6°-77.4° C., IR: 1690 cm-1 ; NMR: (deuterochloroform) 1.20δ (S-3H); 1.07δ (S-3H); 0.90δ (S-3H); 1.32δ-2.70δ (complex multiplets-15H). Isomer B: b.p. 95° C./0.1 mm.Hg. IR: 1690 cm-1, NMR: (deuterochloroform); 1.08δ, 1.05δ (2 singlets-6H); 0.90δ (S-3H) 1.18δ-2.82δ (multiplets-15H).

Workup

  1. additionnitrogen bubbler was added, under nitrogen
  2. customAfter the solution was bubbled with nitrogen for 1 hour
  3. customit was irradiated through a Corning 9700 glass
  4. filtrationfilter for 71/4 hours with an Hanovia 450 watt medium pressure mercury arc
  5. concentrationAt the end of this period, the solution was concentrated in vacuo
  6. customto yield an oil which
  7. distillationwas distilled through a short Vigreux-column
  8. additiona mixture of two major isomers in approximately a 3:1 ratio
  9. customThe two major isomers could be separated by distillation on a spinning band column

Sources & evidence

ORD record
ord-05df0a5ad2b64a9b992c87f5883c3007
Source dataset
uspto-grants-1977_09
Patent number
US04051076

Reaction notes

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