Triphenylethylene → 1,1-Dichloro-2,2,3-triphenylcyclopropane

HRID 2050952Notes

Reaction equation

HRID 2050952 reaction equation
[C:1]1([CH:7]=[C:8]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH:21](Cl)([Cl:23])[Cl:22].[OH-].[Na+]>[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1.O>[Cl:22][C:21]1([Cl:23])[CH:7]([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)[C:8]1([C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Participants

6

Reactant 3

HCID 6025TriphenylethyleneHCID 6212ChloroformHCID 14798Sodium Hydroxide

Product 1

HCID 114391941,1-Dichloro-2,2,3-triphenylcyclopropaneYield 64%

Reagents, catalysts & solvents 2

HCID 66133Benzyl triethylammonium chlorideCatalystHCID 962WaterSolvent

Procedure

Prepared in 64% yield from 3.2 g (12.5 mmol) of triphenylethylene (3.2 g; 12.5 mmol) and 0.25 g (1.1 mmol) benzyltriethylammonium chloride (TEBA) by dissolving in 50 g (419 mmol) CHCl3, stirring rapidly at room temperature, and treating with 27 mL of chilled 50% aqueous NaOH dropwise according to the method of Dehmlow, E. V., et al., S.S. Phase Transfer Catalysis, Verlag Chemie: Deerfield Beach 1980. After stirring 75 h, the resulting mixture was poured onto 150 mL H2O and extracted with CH2Cl2 (2×100 mL). The combined organic layers were washed with 100 mL H2O, dried (Na2SO4), filtered and concentrated. The resulting brown oil was dissolved in boiling petroleum ether, quickly filtered, and allowed to stand at room temperature, yielding 2.7 g (64%) of Compound 4a as a white powder, mp: 106°-107° C. (petroleum ether) (lit. 105°- 107° C.); NMR δ7.23 (m, 15H, ArH), 3.57 (s, 1H, cyclopropyl H); IR (CM-1) 3020, 3000, 1600, 1490, 1435, 860, 775 765, 750, 695; MS (m/z, % base) 342 (M+4), 3.2; 340 (M+2), 6.3; 338 (M+), 10.23; 303 (--Cl), 100; 267 (--Cl, --HCl), 80.7.

Workup

  1. stirringAfter stirring 75 h
  2. extractionextracted with CH2Cl2 (2×100 mL)
  3. washThe combined organic layers were washed with 100 mL H2O
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. dissolutionThe resulting brown oil was dissolved
  8. filtrationquickly filtered
  9. customto stand at room temperature

Sources & evidence

ORD record
ord-74eef1bfa9674592a136f9ddd7516d29
Source dataset
uspto-grants-1991_05
Patent number
US05015666

Reaction notes

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