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

HRID 239039

Reaction equation

HRID 239039 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-866fdd971e574bd28b86e9cdf0c7a400
Source dataset
uspto-grants-2014_02
Patent number
US08642653B2

Linked notes

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