Tetrahydrofuran → HCID 118795, compound

HRID 2057727Notes

Reaction equation

HRID 2057727 reaction equation
[Mg].[O:2]1[CH2:6][CH2:5][CH2:4][CH2:3]1.Br[CH:8](Br)[CH3:9].CO[CH:13](OC)[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20]CCl>C1(C)C=CC=CC=1.BrCC>[CH:3](=[O:2])[CH2:4][CH2:5][CH2:6][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16][CH2:15][CH:14]=[CH:13][CH2:8][CH3:9]

Participants

7

Reactant 4

HCID 8028TetrahydrofuranHCID 112011,1-DibromoethaneHCID 5462224MagnesiumHCID 20330119HCID 20330119, compound

Product 1

HCID 118795HCID 118795, compound

Reagents, catalysts & solvents 2

HCID 6332Ethyl BromideCatalystHCID 1140TolueneSolvent

Procedure

To 0.85 gm of magnesium in a thoroughly dried flask equipped with condensor and magnetic stirrer was added 5 mls of anhydrous tetrahydrofuran and 0.5 ml of dibromo ethane. A solution of 4.5 gms of 1,1-dimethoxy-9-chlorononane in 40 mls of toluene was added dropwise. When addition was half complete, a few drops of bromoethane were added and the addition was continued. The temperature was maintained at 75°±5° for two hours. The Grignard reagent was decanted into another flask and 100 mgs of cuprous chloride (CuCl) catalyst was added, followed by dropwise addition of 3.0 gms of a mixture (approximately 60:40) of 1-chloro-2-pentene and 3-chloro-1-pentene dissolved in 15 mls of toluene. The reaction flask was cooled in a water bath at 20°±5°. Magnesium chloride began to precipitate after ten minutes. The reaction stood overnight at room temperature. 50 mls of 3 N hydrochloric acid was added and the reaction mixture was stirred and heated at reflux for 1 hour. The aqueous layer was separated and washed two times with toluene. The organic layer and the toluene washes were combined and dried over sodium sulphate. The solvents were removed on the rotary evaporator and the residue was distilled at 83° at 0.10 torr yielding 2.3 gms of crude 11-tetradecenal. GLC analysis showed that the contaminating 10-ethyl-11-dodecenal was present in only 11.5%. For physical constants see Example 5.

Workup

  1. additionWhen addition
  2. additionthe addition
  3. temperatureThe temperature was maintained at 75°±5° for two hours
  4. customThe Grignard reagent was decanted into another flask
  5. addition100 mgs of cuprous chloride (CuCl) catalyst was added
  6. additionfollowed by dropwise addition of 3.0 gms of a mixture (approximately 60:40) of 1-chloro-2-pentene and 3-chloro-1-pentene
  7. dissolutiondissolved in 15 mls of toluene
  8. temperatureThe reaction flask was cooled in a water bath at 20°±5°
  9. customto precipitate after ten minutes
  10. addition50 mls of 3 N hydrochloric acid was added
  11. temperatureheated
  12. temperatureat reflux for 1 hour
  13. customThe aqueous layer was separated
  14. washwashed two times with toluene
  15. dry with materialdried over sodium sulphate
  16. customThe solvents were removed on the rotary evaporator
  17. distillationthe residue was distilled at 83° at 0.10 torr

Sources & evidence

ORD record
ord-ff3f2bf49a224bd48274f681f2ff40a4
Source dataset
uspto-grants-1980_07
Patent number
US04212830

Reaction notes

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