tert-BUTYL CHLORIDE → HCID 59172000, compound

HRID 1952424Notes

Reaction equation

HRID 1952424 reaction equation
[CH:1]1[C:13]2[N:12]([CH2:14][CH2:15][CH2:16][P:17](=[O:24])([O:21][CH2:22][CH3:23])[O:18][CH2:19][CH3:20])[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1.[Cl-].[Al+3].[Cl-].[Cl-].Cl[C:30]([CH3:33])([CH3:32])[CH3:31]>>[C:30]([C:8]1[CH:9]=[CH:10][C:11]2[N:12]([CH2:14][CH2:15][CH2:16][P:17](=[O:24])([O:21][CH2:22][CH3:23])[O:18][CH2:19][CH3:20])[C:13]3[C:5]([C:6]=2[CH:7]=1)=[CH:4][C:3]([C:5]([CH3:6])([CH3:13])[CH3:4])=[CH:2][CH:1]=3)([CH3:33])([CH3:32])[CH3:31]

Participants

4

Reactant 3

HCID 10486tert-BUTYL CHLORIDEHCID 6451240Aluminum(III) Chloride2×HCID 59172007HCID 59172007, compound

Product 1

HCID 59172000HCID 59172000, compound

Procedure

Diethyl 3-(9H-carbazol-9-yl)propylphosphonate (1.00 g, 2.89 mmol) was dissolved in 2-chloro-2-methylpropane (5.0 mL) and flushed with N2 for 5 minutes. To this stirred solution was added aluminum chloride (1.16 g, 8.67 mmol) slowly. The solution turned chunky and black with gas bubbles appearing. The reaction was allowed to stir for 25 minutes after adding all the aluminum chloride. It was then quenched with 25 mL water and an extraction performed with water washings followed by 2×20 mL 1 M NaOH washings, then another water washing. The yellow organic layer was kept and dried and the solvent removed under vacuum. A tlc in ethyl acetate showed 4 spots with the brightest (and desired product) being the third spot from the top. A long column was run and the desired product was obtained as a thick yellow oil (447 mg, 34% yield). 1H NMR (400.14 MHz, CD2Cl2) δ 8.10 (d, J=1.6 Hz, 2H), 7.52 (dd, J=8.80, 2.00 Hz, 2H), 7.35 (d, 8.40 Hz, 2H), 4.36 (t, J=7.00 Hz, 2H), 4.08-3.93 (m, 4H), 2.21-2.07 (m, 2H), 1.71 (dt, J=18.14 Hz, 6.00 Hz, 2H), 1.45 (18H), 1.25 (t, J=7.00 Hz, 6H). 13C{1H} NMR (100.61 MHz, CD2Cl2) δ 142.14 (2C), 139.26 (2C), 123.80 (2C), 123.06 (2C), 116.68 (2C), 108.50 (2C), 61.89 (d, J=6.4 Hz, 2C), 43.36 (d, J=15.8 Hz), 34.92 (2C), 32.19 (6C), 23.35 (d, 142.2 Hz), 22.59 (d, J=4.9 Hz), 16.64 (d, J=5.8 Hz, 2C). 31P{1H} NMR (161.97 MHz, CD2Cl2): δ 31.34.

Workup

  1. customflushed with N2 for 5 minutes
  2. customIt was then quenched with 25 mL water
  3. extractionan extraction
  4. customdried
  5. customthe solvent removed under vacuum

Sources & evidence

ORD record
ord-145a6433800e4737b980314d46dda342
Source dataset
uspto-grants-2013_03
Patent number
US08405069B2

Reaction notes

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