1-Bromo-4-chlorobutane → t-Butyl 1-(4-chlorobutyl)-1-cyclopropanecarboxylate

HRID 968995Notes

Reaction equation

HRID 968995 reaction equation
Br[CH2:2][CH2:3][CH2:4][CH2:5][C:6]1([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:8][CH2:7]1.C1(C(OC(C)(C)C)=O)CC1.BrCCCC[Cl:31].[Li+].CC([N-]C(C)C)C>>[Cl:31][CH2:2][CH2:3][CH2:4][CH2:5][C:6]1([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:8][CH2:7]1

Participants

5

Reactant 4

HCID 813641-Bromo-4-chlorobutaneHCID 2724682Lithium diisopropylamideHCID 13676038tert-Butyl cyclopropanecarboxylateHCID 21932036Tert-Butyl 1-(4-bromobutyl)cyclopropanecarboxylate

Product 1

HCID 21932032t-Butyl 1-(4-chlorobutyl)-1-cyclopropanecarboxylate

Procedure

Compound 104a was prepared, likewise the procedure described for 103b, starting from t-butyl cyclopropanecarboxylate (Kohlrausch, K. W. F. et al. Z. Elektrochem. Angew. Phys. Chem, 1937, 43, 282-285) (12.5 g, 88 mmol), 1-bromo-4-chlorobutane (13.7 mL, 117 mmol) and LDA (prepared from BuLi (2.5M in hexanes, 37 mL, 92.5 mmol) and iPr2NH (12.3 mL, 88 mmol, distilled from NaOH)) to give, after purification by fractional distillation under reduced pressure, 104a (10.73 g 52%) as a colorless oil. bp: T=57-61° C. (p=0.001 mbar). 1H NMR: δ 3.52 (t, J=6.6 Hz, 2H), 1.76 (quintet, J=6.8 Hz, 2H), 1.64-1.54 (m, 2H), 1.51-1.46 (m, 2H), 1.42 (s, 9H), 1.12 (dd, J=6.6, 3.9 Hz, 2H), 0.60 (dd, J=6.6, 3.9 Hz, 2H). 13C NMR: δ 173.9, 80.0, 45.1, 33.6, 32.9, 28.2 (3×), 25.3, 24.2, 15.4 (2×). HRMS calcd for C12H22ClO2 (MH+): 233.1308, found: 233.1308.

Workup

  1. customto give
  2. customafter purification
  3. distillationby fractional distillation under reduced pressure, 104a (10.73 g 52%) as a colorless oil
  4. customT=57-61° C. (p=0.001 mbar)

Sources & evidence

ORD record
ord-8093fe61d00f4283a3d0c16d808fd440
Source dataset
uspto-grants-2007_12
Patent number
US07304093B2

Reaction notes

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