Acetylene → 1-[1-triphenylmethyl-1H-imidazol-4-yl]-6-cyclohexyl-3-hexyne

HRID 1276464Notes

Reaction equation

HRID 1276464 reaction equation
[C:1]1([C:7]([C:52]2[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=2)([C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)N2C(C(CCC(OP(OCC)(OCC)=O)=C(S(C3C=CC(C)=CC=3)(=O)=O)CCC3CCCCC3)=O)=CN=C2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.CN(P([N:66]([CH3:68])[CH3:67])(N(C)C)=O)C.[Cl-].[NH4+:70].[CH:71]#[CH:72]>C1COCC1.C(Cl)(Cl)Cl>[C:46]1([C:7]([C:52]2[CH:53]=[CH:54][CH:55]=[CH:56][CH:57]=2)([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[N:66]2[CH:67]=[C:71]([CH2:72][CH2:49][C:48]#[C:47][CH2:46][CH2:7][CH:1]3[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]3)[N:70]=[CH:68]2)[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1

Participants

7

Reactant 4

HCID 6326AcetyleneHCID 12679HexamethylphosphoramideHCID 25517Ammonium ChlorideHCID 54072701HCID 54072701, compound

Product 1

HCID 184283751-[1-triphenylmethyl-1H-imidazol-4-yl]-6-cyclohexyl-3-hexyne

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

1-[1-Triphenylmethyl-5-imidazoyl]-3-(diethoxyphosphinyl)oxy-4-p-toluenesulfonyl-6-cyclohexyl-3-hexene (14.5 g, 0.018 mol) was dissolved in dry THF (150 ml) and HMPA (10 ml) at room temperature under N2. Sml2 (0.1M solution in THF) was added to the reaction in 50 ml portions via syringe. Atotal of 400 ml of 0.1M Sml2 was added. After the last 50 ml portion was added, the blue reaction mixture was stirred for 1 hour. The reaction mixture was added to 500 ml of a saturated solution of ammonium chloride and extracted with ethyl acetate (2×500 ml). The ethyl acetate layer was washed with brine (250 ml), water (2×400 ml) and brine (250 ml). The ethyl acetate layer was separated, dried over MgSO4, filtered and evaporated in vacuo to give a yellow oil. The crude acetylene was taken up in 25 ml of CHCl3 and filtered through a pad of silica gel (200 g) using 1 liter of ethyl acetate/hexanes (2:8). The filtrate was evaporated in vacuo to afford a viscous yellow oil which solidified upon standing. The solid was triturated with hexanes, filtered and washed with hexanes to give 5.5 g of 1-[1-triphenylmethyl-1H-imidazol-4-yl]-6-cyclohexyl-3-hexyne.

Workup

  1. customat room temperature
  2. additionAtotal of 400 ml of 0.1M Sml2 was added
  3. additionAfter the last 50 ml portion was added
  4. customthe blue reaction mixture
  5. extractionextracted with ethyl acetate (2×500 ml)
  6. washThe ethyl acetate layer was washed with brine (250 ml), water (2×400 ml) and brine (250 ml)
  7. customThe ethyl acetate layer was separated
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. customevaporated in vacuo
  11. customto give a yellow oil
  12. filtrationfiltered through a pad of silica gel (200 g)
  13. customThe filtrate was evaporated in vacuo
  14. customto afford a viscous yellow oil which
  15. customThe solid was triturated with hexanes
  16. filtrationfiltered
  17. washwashed with hexanes

Sources & evidence

ORD record
ord-42f6835692d64808b28f62eee1366fc2
Source dataset
uspto-grants-2000_12
Patent number
US06166060

Reaction notes

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