Dichloromethane → HCID 131730837, compound

HRID 39113Notes

Reaction equation

HRID 39113 reaction equation
C([Li])CCC.[CH:6]1[C:18]2[CH2:17][C:16]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[C:10]=2[CH:9]=[CH:8][CH:7]=1.[CH2:19]([O:21][CH:22]([O:25][CH2:26][CH3:27])[CH2:23]Br)[CH3:20].C(Cl)Cl>C(OCC)C>[CH2:19]([O:21][CH:22]([O:25][CH2:26][CH3:27])[CH2:23][C:6]1[C:18]2[CH2:17][C:16]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[C:10]=2[CH:9]=[CH:8][CH:7]=1)[CH3:20]

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 6853FluoreneHCID 74852Ethane, 2-bromo-1,1-diethoxy-HCID 178418339Butyllithium

Product 1

HCID 131730837HCID 131730837, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
25 °C

Procedure

A solution of n-butyllithium (100.0 mL, 1.6 M, 0.161 mol) in hexanes was added dropwise to a cooled (0° C.) solution of fluorene (26.75 g, 0.161 mol) in 200 mL of diethyl ether. The reaction solution turned orange and was warmed to 25° C. for 30 minutes. The orange solution was added dropwise to a cooled (0° C.) solution of bromoacetaldehyde diethylacetal (25.0 mL, 0.161 mol) in 50 mL of diethyl ether. The reaction solution was stirred for 12 hours and the solvent then removed in vacuo leaving purple oil. Methylene chloride (300 mL) was added to the residue to give a cloudy white mixture, which was extracted with deionized water (5×100 mL). The yellow organic layer was dried over Na2SO4 and the solids were then separated by filtration. Solvent was removed from the filtrate in vacuo to leave a pale yellow oil which solidified to a yellow waxy solid upon standing. Yield: 42.2 g, 0.149 mol (93%). 1H NMR (CDCl3, 600 MHz): δ 7.73 (d, 3JHH=7.8 Hz, 2H, flu-H4), 7.54 (d, 3JHH=7.8 Hz, 2H, flu-H1), 7.34 (t, 3JHH=7.2 Hz, 2H, flu-H3), 7.28 (t, 3JHH=7.2 Hz, 2H, flu-H2), 4.69 (t, 3JHH=6.0 Hz, 1H, CH), 4.08 (t, 3JHH=7.2 Hz, 1H, flu-CH), 3.52 (dm, 4H, OCH2CH3), 2.21 (dd, 2H, CH2), 1.13 (t, 3JHH=7.2 Hz, 6H, OCH2CH3). 13C{1H} NMR (CDCl3, 150.8 MHz): 147.25 (s, C1-a), 140.81 (s, C4a), 126.96 (s, C2), 126.82 (s, C3), 124.73 (s, C1), 119.78 (s, C4), 101.41 (s, CH), 61.45 (s, OCH2CH3), 43.93 (s, C9), 37.49 (s, CH2), 15.27 (s, OCH2CH3). MS (ES) m/z (assignment, relative intensity): 305.2 (C19H22O2Na, [M+Na]+, 100%). Anal. Calcd. for C19H22O2: C, 80.82; H, 7.85. Found: C, 80.89; H, 8.09.

Workup

  1. additionThe orange solution was added dropwise to
  2. customthe solvent then removed in vacuo
  3. customleaving purple oil
  4. customto give a cloudy white mixture, which
  5. extractionwas extracted with deionized water (5×100 mL)
  6. dry with materialThe yellow organic layer was dried over Na2SO4
  7. customthe solids were then separated by filtration
  8. customSolvent was removed from the filtrate in vacuo
  9. customto leave a pale yellow oil which

Sources & evidence

ORD record
ord-e9ec76f82cd648198c7032390589201c
Source dataset
uspto-grants-2013_09
Patent number
US08524846B1

Reaction notes

Loading…