Hydrochloric Acid → (E)-4-(2,2-difluorovinyl)-4'-(prop-1-en-1-yl)-1,1'-bi(cyclohexane)

HRID 1614840Notes

Reaction equation

HRID 1614840 reaction equation
[F:1][C:2]([F:5])(Br)Br.C(N(P(N(CC)CC)N(CC)CC)CC)C.[CH:22](/[CH:25]1[CH2:30][CH2:29][CH:28]([CH:31]2[CH2:36][CH2:35][CH:34]([CH:37]=O)[CH2:33][CH2:32]2)[CH2:27][CH2:26]1)=[CH:23]\[CH3:24].Cl>C1COCC1>[F:1][C:2]([F:5])=[CH:37][CH:34]1[CH2:35][CH2:36][CH:31]([CH:28]2[CH2:29][CH2:30][CH:25](/[CH:22]=[CH:23]/[CH3:24])[CH2:26][CH2:27]2)[CH2:32][CH2:33]1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 6382DibromodifluoromethaneHCID 75292Hexaethylphosphorous triamideHCID 19781281(E)-4'-(prop-1-en-1-yl)-[1,1'-bi(cyclohexane)]-4-carbaldehyde

Product 1

HCID 71009768(E)-4-(2,2-difluorovinyl)-4'-(prop-1-en-1-yl)-1,1'-bi(cyclohexane)

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Difluorodibromomethane (29.9 g) was dissolved in THF (100 ml), and then a tris(diethylamino)phosphine (63.4 g) THF (20 ml) solution and an (E)-4′-(prop-1-en-1-yl)-[1,1′-bi(cyclohexane)]-4-carbaldehyde (20.0 g) THF (20 ml) solution were sequentially added dropwise in an ice bath under a nitrogen atmosphere. After completion of the reaction, 1 N hydrochloric acid was added, and extraction was carried out with toluene. An organic layer was washed with a saturated aqueous solution of sodium chloride, a saturated aqueous solution of sodium hydrogencarbonate and water, and then the resultant solution was dried over anhydrous magnesium sulfate and concentrated under reduced pressure, and thus a colorless oily matter was obtained. The resultant material was subjected to silica gel column chromatography (heptane) and recrystallization using Solmix A-11 (registered trademark) (Japan Alcohol Trading Co., Ltd.), and thus compound (1-B) was obtained as a white needle crystal (7.7 g).

Workup

  1. additionwas added
  2. extractionextraction
  3. washAn organic layer was washed with a saturated aqueous solution of sodium chloride
  4. dry with materiala saturated aqueous solution of sodium hydrogencarbonate and water, and then the resultant solution was dried over anhydrous magnesium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customthus a colorless oily matter was obtained
  7. customThe resultant material was subjected to silica gel column chromatography (heptane) and recrystallization

Sources & evidence

ORD record
ord-de60e484c8ff44a7a8452bfe3184add7
Source dataset
uspto-grants-2014_07
Patent number
US08765011B2

Reaction notes

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