Dichloromethane → Indenyl Acetaldehyde Diethylacetal

HRID 39114

Reaction equation

HRID 39114 reaction equation
C([Li])CCC.[CH2:6]1[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[CH:8]=[CH:7]1.[CH2:15]([O:17][CH:18]([O:21][CH2:22][CH3:23])[CH2:19]Br)[CH3:16].C(Cl)Cl>C(OCC)C>[CH2:15]([O:17][CH:18]([O:21][CH2:22][CH3:23])[CH2:19][CH:6]1[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[CH:8]=[CH:7]1)[CH3:16]

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 7219IndeneHCID 74852Ethane, 2-bromo-1,1-diethoxy-HCID 178418339Butyllithium

Product 1

HCID 89778594Indenyl Acetaldehyde Diethylacetal

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
25 °C

Procedure

A solution of n-butyllithium (20.0 mL, 1.6 M, 32.2 mmol) in hexanes was added dropwise to a cooled (0° C.) solution of indene (5.35 g, 32.2 mmol) in 50 mL of diethyl ether. The reaction solution turned yellow and was warmed to 25° C. for 30 minutes. This yellow solution was added dropwise to a cooled (0° C.) solution of bromoacetaldehyde diethylacetal (5.00 mL, 32.2 mmol) in 50 mL of diethyl ether. The reaction mixture turned bright red after warming to 25° C. and was stirred for 12 hours, during which time it darkened to brown. The solvent was then removed in vacuo leaving brown oil. Methylene chloride (100 mL) was added to give a cloudy white mixture which was extracted with deionized water (3×100 mL). The brown organic layer was dried over Na2SO4 and then solids were separated by filtration. Solvent was removed from the filtrate in vacuo resulting in brown oil. Yield: 5.48 g, 23.5 mmol (85%). 1H NMR (CDCl3, 600 MHz): δ 7.43 (d, 3JHH=7.2 Hz, 1H, H4), 7.35 (d, 3JHH=7.8 Hz, 1H, H7), 7.25 (t, 3JHH=7.2 Hz, 1H, H5), 7.19 (t, 3JHH=7.2 Hz, 1H, H6), 6.80 (dd, 1H, H2), 6.61 (dd, 1H, H3), 4.68 (m, 1H, CH), 3.69 (dm, 2H, OCH2CH3), 3.56 (m, 1H, H1), 3.52 (dm, 2H, OCH2CH3), 2.22 (m, 1H, CH2), 1.71 (m, 1H, CH2), 1.24 (t, 3JHH=7.2 Hz, 3H, OCH2CH3), 1.19 (t, 3JHH=7.2 Hz, 3H, OCH2CH3). 13C{1H} NMR (CDCl3, 150.8 MHz): 147.51 (s, C7a), 144.13 (s, C3a), 139.13 (s, C3), 130.79 (s, C2), 126.56 (s, C5), 124.73 (s, C6), 123.00 (s, C4), 121.05 (s, C7), 102.10 (s, CH), 61.44 (s, OCH2CH3), 61.23 (s, OCH2CH3), 46.66 (s, C1), 35.51 (s, CH2), 15.38 (s, OCH2CH3). MS (ES) m/z (assignment, relative intensity): 255.2 (C15H20O2Na, [M+Na]+, 100%). Anal. Calcd. for C15H20O2: C, 77.54; H, 8.68. Found: C, 77.34; H, 8.76.

Workup

  1. additionThis yellow solution was added dropwise to
  2. temperatureafter warming to 25° C.
  3. customThe solvent was then removed in vacuo
  4. customleaving brown oil
  5. customto give a cloudy white mixture which
  6. extractionwas extracted with deionized water (3×100 mL)
  7. dry with materialThe brown organic layer was dried over Na2SO4
  8. customsolids were separated by filtration
  9. customSolvent was removed from the filtrate in vacuo
  10. customresulting in brown oil

Sources & evidence

ORD record
ord-7cffac81e2d54a4c8667f812aece074d
Source dataset
uspto-grants-2013_09
Patent number
US08524846B1

Linked notes

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