1-Bromoundecane → HCID 14892326, compound

HRID 840660Notes

Reaction equation

HRID 840660 reaction equation
[Mg].Br[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH3:13].Cl.[Cl:15][C:16]1[CH:21]=[CH:20][N:19]=[CH:18][CH:17]=1.Cl[C:23]([O:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)=[O:24]>C(OCC)C.C1COCC1>[Cl:15][C:16]1[CH:21]=[CH:20][N:19]([C:23]([O:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)=[O:24])[CH:18]([CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH3:13])[CH:17]=1

Participants

7

Reactant 4

HCID 127441-BromoundecaneHCID 15891Phenyl chloroformateHCID 818524-Chloropyridine hydrochlorideHCID 5462224Magnesium

Product 1

HCID 14892326HCID 14892326, compoundYield 88%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a stirred mixture of magnesium turnings (0.584, 24 mmol) in 40 ml of anhydrous diethyl ether was added 1-bromoundecane (5.36 mL, 24 mmol). After a self sustained reflux period of 10 minutes, the solution was refluxed an additional 45 min and then allowed to cool to room temperature. The newly formed Grignard was canulated in a stirred solution of 4-chloropyridine hydrochloride (1.5 g, 10 mmol) in 80 ml of THF at −78° C. After 20 minutes, phenyl chloroformate (1.26 ml, 10 mmol) was added dropwise. Stirring was continued for 30 min. longer at −78° C. The cooling bath was removed and the reaction mixture was allowed to stir for 30 minutes longer while slowly warming to room temperature. 20% NH4Cl (30 ml) and ether (40 ml) were added and the layers separated, and the aqueous layer was extracted with two 25 ml portions of ether. The combined organic extracts were washed successively with 25 ml portions of saturated CuSO4, water, saturated NaHCO3, and brine. The organic phase was dried with MgSO4, the solvent was evaporated, to yield the crude product as a yellow oil. Purification by column chromatography with 5% EtOAc in hexanes afforded 3.4 g (88%) of the product as a clear oil which was homogeneous by TLC analysis. 1H NMR (300 MHz) δ7.45-7.10 (m, 5 H), 6.94-6.86 (pair of d, 1H), 5.68 (d, 1 H), 5.41-5.29 (dd, 1 H), 5.02-4.85 (m, 1 H), 1.83-1.40 (m, 2 H), 1.24 (br s, 18 H), 0.88 (t, 3H); FT-IR (neat) 2954, 2923, 2852, 1735, 1635, 1592, 1495, 1471, 1332, 1202, 1050 cm−1.

Workup

  1. temperatureAfter a self sustained reflux period of 10 minutes
  2. temperaturethe solution was refluxed an additional 45 min
  3. waitwas continued for 30 min. longer at −78° C
  4. customThe cooling bath was removed
  5. stirringto stir for 30 minutes longer
  6. temperaturewhile slowly warming to room temperature
  7. addition20% NH4Cl (30 ml) and ether (40 ml) were added
  8. customthe layers separated
  9. extractionthe aqueous layer was extracted with two 25 ml portions of ether
  10. washThe combined organic extracts were washed successively with 25 ml portions of saturated CuSO4, water, saturated NaHCO3, and brine
  11. dry with materialThe organic phase was dried with MgSO4
  12. customthe solvent was evaporated
  13. customto yield the crude product as a yellow oil
  14. customPurification by column chromatography with 5% EtOAc in hexanes

Sources & evidence

ORD record
ord-a5fe0de4901b4cb5b70dcddc9090989f
Source dataset
uspto-grants-2002_04
Patent number
US06369078B1

Reaction notes

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