Methyl iodide → HCID 178436318, compound

HRID 370694Notes

Reaction equation

HRID 370694 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][C:6]([C@H:9]2[CH2:14][CH2:13][C@H:12]([CH2:15][CH2:16][CH2:17][CH2:18][CH3:19])[CH2:11][CH2:10]2)=[CH:5][CH:4]=1)#[CH:2].[CH2:20]([Li])CCC.CN(C)P(=O)(N(C)C)N(C)C.CI>O1CCCC1.CCCCCC.O>[C:1]([C:3]1[CH:8]=[CH:7][C:6]([C@H:9]2[CH2:14][CH2:13][C@H:12]([CH2:15][CH2:16][CH2:17][CH2:18][CH3:19])[CH2:11][CH2:10]2)=[CH:5][CH:4]=1)#[CH:2].[C:1]([C:3]1[CH:8]=[CH:7][C:6]([C@H:9]2[CH2:14][CH2:13][C@H:12]([CH2:15][CH2:16][CH2:17][CH2:18][CH3:19])[CH2:11][CH2:10]2)=[CH:5][CH:4]=1)#[C:2][CH3:20]

Participants

9

Reactant 4

HCID 6328Methyl iodideHCID 12679HexamethylphosphoramideHCID 178418339ButyllithiumHCID 178436318HCID 178436318, compound

Product 2

HCID 178436318HCID 178436318, compoundYield 31.7%HCID 178439120HCID 178439120, compoundYield 22.4%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-20 °C

Procedure

A solution of 2.55 g of 1-ethynyl-4-(trans-4-pentylcyclohexyl)benzene (prepared according to Example 3) in 90 ml of absolute tetrahydrofuran was placed at -20° C. in a sulphonation flask under argon gasification and treated within 5 minutes with 11.0 ml of a 1.0N solution of butyl lithium in hexane. The clear yellow mixture was subsequently stirred at -20° C. for a further 30 minutes and then treated in sequence with 10 ml of hexamethylphosphoric acid triamide and 747 μl of methyl iodide. After warming to room temperature, the now dark violet mixture was stirred for a further 4 hours, subsequently poured into 150 ml of water and extracted three times with 150 ml of petroleum ether each time. The organic phases were washed twice with 200 ml of water each time, dried over magnesium sulphate and concentrated. Low-pressure chromatography (0.5 bar) of the residue (3.01 g) on silica gel with hexane gave in sequence 806 mg (31.7%) of 1-ethynyl-4-(trans-4-pentylcyclohexyl)benzene, 431 mg (16.3%) of a mixture of 1-ethynyl-4-(trans-4-pentylcyclohexyl)benzene and 1-(1-propynyl)-4-(trans-4-pentylcyclohexyl)benzene and 601 mg (22.4 %) of 1-(1-propynyl)-4-(trans-4-pentylcyclohexyl)benzene. A recrystallization of the last fraction from 50 ml of methanol yielded 464 mg of 1-(1-propynyl)-4-(trans-4-pentylcyclohexyl)benzene as colourless crystals; m.p. (C-N) 41.6° C., cl.p. (N-I) 64.9° C.; η(22° C.)=23 cp: η(45° C.)=7.7 cp.

Workup

  1. temperatureAfter warming to room temperature
  2. stirringthe now dark violet mixture was stirred for a further 4 hours
  3. extractionextracted three times with 150 ml of petroleum ether each time
  4. washThe organic phases were washed twice with 200 ml of water each time
  5. dry with materialdried over magnesium sulphate
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-4141ed48ee0b42549146b646f99fb029
Source dataset
uspto-grants-1985_07
Patent number
US04528114

Reaction notes

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