Propylene → HCID 12476417, compound

HRID 855897Notes

Reaction equation

HRID 855897 reaction equation
C([Mg]Br)C=C.[CH2:6]([B:9]([CH2:13][CH:14]=[CH2:15])[CH2:10][CH:11]=[CH2:12])[CH:7]=[CH2:8].[CH2:16]([O:19][CH3:20])[C:17]#[CH:18].C=CC>C(OCC)C.CO>[B:9]12[CH2:13][CH:14]3[CH2:15][CH:11]([CH2:12][CH:7]([CH2:8]3)[CH2:6]1)[CH2:10]2.[CH2:18]1[CH2:20][O:19][CH2:16][CH2:17]1

Participants

7

Reactant 4

HCID 8252PropyleneHCID 693933-MethoxypropyneHCID 5326206TRIALLYLBORANEHCID 178455850HCID 178455850, compound

Product 1

HCID 12476417HCID 12476417, compoundYield 52%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 3283Diethyl EtherSolvent

Procedure

Under Ar atmosphere and vigorous stirring, to 100 ml (1.0M) of allylmagnesium bromide in diethyl ether was added dropwise 4.8 g of borontrifloride diethyl ether. After refluxing for 30 min, the mixture was permitted to stand over night. The solution layer was transferred to another flask under Ar. The diethyl ether was removed by distillation at 60° C. under normal pressure. The triallyl borane was distilled from the mixture under reduced pressure to yield 2.7 g (60%). To a 100 ml flask preheated to 130° C. was added 2.7 g of triallyl borane. After stirring for 5 min was added 1.4 g of methyl propargyl ether. The mixture was stirred for 1 hour then cooled down to room temperature. To the mixture was added 0.7 ml of methanol and stirred for 15 min after the propene gas evacuated completely. To the remaining oil was added 20 ml (1.0 M) of borane THF complex in THF solution. The mixture was refluxed at 80° C. for 2 hours. The THF was then removed under vacuum at room temperature. The pure 1-boraadamantane THF complex was obtained from the white solid residue via sublimation under vacuum in 2.0 g (yield: 52%). The spectra data were as follows: 1H-NMR (25° C. in CDCl3) δ 3.4 ppm (t, 4H, THF CH2-O), δ 2.7 ppm (m, 3H, CH), δ 1.9 ppm (t, 4H, THF CH2), δ 1.1 ppm (m, CH2). 11B-NMR (25° C. in CDCl3) δ 12.58 ppm (s); 13C-NMR (25° C. in CDCl3) δ 24.1 ppm (s, THF CH2), δ 30.4 ppm (b, CH2-B), δ 34.9 ppm (s, CH), δ 40.8 ppm (s, CH2), δ 68.2 ppm (s, THF CH2—O).

Workup

  1. temperatureAfter refluxing for 30 min
  2. waitto stand over night
  3. customThe solution layer was transferred to another flask under Ar
  4. customThe diethyl ether was removed by distillation at 60° C. under normal pressure
  5. distillationThe triallyl borane was distilled from the mixture under reduced pressure
  6. customto yield 2.7 g (60%)
  7. customTo a 100 ml flask preheated to 130° C.
  8. stirringThe mixture was stirred for 1 hour
  9. customevacuated completely
  10. additionTo the remaining oil was added 20 ml (1.0 M) of borane THF complex in THF solution
  11. temperatureThe mixture was refluxed at 80° C. for 2 hours
  12. customThe THF was then removed under vacuum at room temperature
  13. customThe pure 1-boraadamantane THF complex was obtained from the white solid residue via sublimation under vacuum in 2.0 g (yield: 52%)

Sources & evidence

ORD record
ord-57ebecebcf6a4d088f63ac99338046e8
Source dataset
uspto-grants-2007_08
Patent number
US07262257B2

Reaction notes

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