Water → 3beta-(4-Chlorophenyl)-2beta-[(E)-2-chlorovinyl]tropane

HRID 326414Notes

Reaction equation

HRID 326414 reaction equation
C([Li])CCC.[Cl-].[Cl:7][CH2:8][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cl:28][C:29]1[CH:34]=[CH:33][C:32]([C@H:35]2[CH2:41][C@H:40]3[N:42]([CH3:43])[C@H:37]([CH2:38][CH2:39]3)[C@H:36]2[CH:44]=O)=[CH:31][CH:30]=1.O>CCOCC>[Cl:28][C:29]1[CH:34]=[CH:33][C:32]([C@H:35]2[CH2:41][C@H:40]3[N:42]([CH3:43])[C@H:37]([CH2:38][CH2:39]3)[C@H:36]2/[CH:44]=[CH:8]/[Cl:7])=[CH:31][CH:30]=1

Participants

6

Reactant 4

HCID 962WaterHCID 197823(Chloromethyl)triphenylphosphonium chlorideHCID 100156433beta-(4-Chlorophenyl)-2beta-formyltropaneHCID 178418339Butyllithium

Product 1

HCID 100401943beta-(4-Chlorophenyl)-2beta-[(E)-2-chlorovinyl]tropaneYield 20.5%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
0 °C

Procedure

A solution of butyllithium (0.32 mL, 2.5M in hexane, 0.68 mmol) was added to a stirred solution of chloromethyltriphenylphosphonium chloride (237 mg, 0.68 mmol) in dry EtzO (5 mL) at room temperature under N2 atmosphere. The resulting orange mixture was stirred for 30 min at that temperature, and then crude 3β-(4-chlorophenyl)-2β-formyltropane (60 mg, 0.23 mmol) in dry ether (4 mL) was added dropwise. The mixture was stirred at room temperature for 2 hr, cooled at 0° C., mixed with water (2 mL), and extracted with ethyl acetate. The organic layer was dried over Na2SO4 and concentrated in vacuum. The crude product was purified by flash column chromatography on silica gel saturated with NH3 eluting with hexane:ethyl acetate=1:1. Removal of the solvent gave 2d (14 mg, 20%); [α]D22 =-124° (c=0.52, CHCl3); IR (thin film) 3061, 2930, 2798, 1618, 1492, 941, 925 cm-1 ; 1H NMR (CDCl3, 300 MHz) δ 7.23 (d, 2H, J=8.5 Hz), 7 (d, 2H, J=8.5 Hz), 6.14 (dd, 1H, J=13.4, 10 Hz), 5.47 (d, 1H, J=13.4 Hz), 3.27 (s, 1H), 3.03 (m, 2H), 2.28 (m, 1H), 2.22 (s, 3H), 2.18-1.64 (m, 6H); 13C NMR (CDCl3, 75.46 MHz) 141.14, 133.88, 131.75, 129.34, 128.17, 117.55, 67.29, 61.99, 49.64, 41.96, 36.61, 34.50, 26.44, 24.98; mass spectrum, m/z 297 (M+, 37Cl), 195 (M+, 35Cl), 260, 218, 141, 97, 82.

Workup

  1. stirringThe mixture was stirred at room temperature for 2 hr
  2. extractionextracted with ethyl acetate
  3. dry with materialThe organic layer was dried over Na2SO4
  4. concentrationconcentrated in vacuum
  5. customThe crude product was purified by flash column chromatography on silica gel saturated with NH3 eluting with hexane
  6. customRemoval of the solvent

Sources & evidence

ORD record
ord-8ed56e3b3c79465bb85ba4e4b102d6ef
Source dataset
uspto-grants-1993_12
Patent number
US05268480

Reaction notes

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