Butyl iodide → HCID 178442125, compound

HRID 370695Notes

Reaction equation

HRID 370695 reaction equation
Br[C:2](Br)=[CH:3][C:4]1[CH:9]=[CH:8][C:7]([CH2:10][CH2:11][C@H:12]2[CH2:17][CH2:16][C@H:15]([CH2:18][CH2:19][CH2:20][CH2:21][CH3:22])[CH2:14][CH2:13]2)=[CH:6][CH:5]=1.[CH2:24]([Li])[CH2:25][CH2:26]C.CN(C)P(=O)(N(C)C)N(C)C.C(I)CCC>O1CCCC1.CCCCCC.O>[C:3]([C:4]1[CH:9]=[CH:8][C:7]([CH2:10][CH2:11][C@H:12]2[CH2:17][CH2:16][C@H:15]([CH2:18][CH2:19][CH2:20][CH2:21][CH3:22])[CH2:14][CH2:13]2)=[CH:6][CH:5]=1)#[C:2][CH2:24][CH2:25][CH3:26]

Participants

8

Reactant 4

HCID 10962Butyl iodideHCID 12679HexamethylphosphoramideHCID 178418339ButyllithiumHCID 178444401HCID 178444401, compound

Product 1

HCID 178442125HCID 178442125, compoundYield 81%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

A solution of 1.42 g of β,β-dibromo-p-[2-(trans-4-pentylcyclohexyl)ethyl]styrene (prepared according to Example 5) in 32 ml of absolute tetrahydrofuran was placed at about 31 45° C. in a sulphonation flask under argon gasification and treated within 5 minutes with 8.0 ml of a 1.2N solution of butyl lithium in hexane. After completed addition, the reaction mixture was stirred at this temperature for a further 90 minutes, before it was treated at -40° C. in sequence with 3.2 ml of hexamethylphosphoric acid triamide and 0.62 ml of butyl iodide. After warming to room temperature, the mixture was stirred for a further 24 hours, subsequently poured into 50 ml of water and extracted three times with 50 ml of petroleum ether each time. The organic phases were washed a further twice with 50 ml of water each time and once with 50 ml of saturated sodium chloride solution, dried over magnesium sulphate and concentrated. Low-pressure chromatography (0.5 bar) of the residue (1.07 g) on silica gel with hexane as the eluant gave 840 mg (81%) of 1-(1-pentynyl)-4-[2-(trans-4-pentylcyclohexyl)ethyl]benzene as colourless crystals (purity according to gas chromatography 98.3%). Recrystallization from 75 ml of methanol yielded 634 mg of 1-(1-pentynyl)-4-[2-(trans-4-pentylcyclohexyl)ethyl]benzene with m.p. (C-I) 37.8° C. and cl.p. (S-I) 30.9° C.

Workup

  1. additionaddition
  2. stirringthe mixture was stirred for a further 24 hours
  3. extractionextracted three times with 50 ml of petroleum ether each time
  4. washThe organic phases were washed a further twice with 50 ml of water each time
  5. dry with materialonce with 50 ml of saturated sodium chloride solution, dried over magnesium sulphate
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-2b5b9d8f9ac84cb99e33f3c658e55fd7
Source dataset
uspto-grants-1985_07
Patent number
US04528114

Reaction notes

Loading…