Dibromomethane → 1-Bromo-2-cyano-2-(2-ethoxyphenyl)heptane

HRID 330303Notes

Reaction equation

HRID 330303 reaction equation
[H-].[Na+].[CH2:3]([O:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=1[CH:12]([CH2:15][CH2:16][CH2:17][CH2:18][CH3:19])[C:13]#[N:14])[CH3:4].[CH2:20](Br)[Br:21].CCOCC>CN(C)C=O.O>[Br:21][CH2:20][C:12]([C:13]#[N:14])([C:7]1[CH:8]=[CH:9][CH:10]=[CH:11][C:6]=1[O:5][CH2:3][CH3:4])[CH2:15][CH2:16][CH2:17][CH2:18][CH3:19]

Participants

7

Reactant 4

HCID 3024DibromomethaneHCID 3283Diethyl EtherHCID 24758Sodium hydrideHCID 146993902-(2-Ethoxyphenyl)heptanenitrile

Product 1

HCID 146993911-Bromo-2-cyano-2-(2-ethoxyphenyl)heptaneYield 97.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent3×

Procedure

A 200 ml three-neck flask fitted with a reflux condenser, nitrogen inlet, thermometer and addition funnel was charged with 1.8 grams (0.045 moles, 1.28 ec.) of 60% NaH, washed 2×40 ml of hexane, in 30 ml of dimethyl formamide (DMF). While stirring at room temperature, 1.41 grams of 35% KH (with removal of the mineral oil before washing with hexane, assumed 100% KH, 0.035 moles, 1.0 ec.) in 20 ml of DMF was added. To the reaction was added 8.10 grams (0.0350 moles, 1.0 ec.) of 2-(2-ethoxyphenyl)heptanenitrile in 25 ml of DMF. After stirring at room temperature for 1 hour, 9.15 grams (0.0525 moles, 1.5 eg.) of CH2Br2 in 25 ml of DMF was added dropwise over 10 minutes. The reaction exothermed slightly and was stirred at room temperature overnight after which GLC indicated the reaction was 80% product. An additional 0.7 g of 100% KH (0.5 ec.) was added in 20 ml of DMF, after washing with 20 ml of hexane, and this was followed by an additional 3.0 grams of CH2Br2The reaction was stirred for an additional 3 hours and was complete by GLC. Workup with ether and water gave after concentration 10.97 grams of a thick oil (97.2% yield) which was used directly in the coupling procedure.

Workup

  1. customA 200 ml three-neck flask fitted with a reflux condenser, nitrogen inlet
  2. additionthermometer and addition funnel
  3. washwashed 2×40 ml of hexane
  4. custom1.41 grams of 35% KH (with removal of the mineral oil
  5. washbefore washing with hexane
  6. addition) in 20 ml of DMF was added
  7. stirringAfter stirring at room temperature for 1 hour
  8. stirringwas stirred at room temperature overnight after which GLC
  9. washafter washing with 20 ml of hexane
  10. stirringwas stirred for an additional 3 hours

Sources & evidence

ORD record
ord-79976c51ef6347ecb7abb40a9add796a
Source dataset
uspto-grants-1990_01
Patent number
US04895865

Reaction notes

Loading…