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

HRID 646785Notes

Reaction equation

HRID 646785 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 (n, 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-ad7205d5f4c6499bbe13ad04b8337ea5
Source dataset
uspto-grants-2010_04
Patent number
US07705177B2

Reaction notes

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