Water → HCID 76044689, compound

HRID 2170255Notes

Reaction equation

HRID 2170255 reaction equation
CC(C)([O-])C.[K+].[CH3:7][C:8]([CH2:19][CH2:20][CH:21]=[C:22]([CH3:24])[CH3:23])=[CH:9][CH2:10]P(OCC)(=O)OCC.[CH3:25][CH:26]([CH:29]([O:32][CH3:33])[O:30][CH3:31])[CH:27]=O.O>O1CCCC1.CCOCC>[CH3:25][CH:26]([CH:27]=[CH:10][CH:9]=[C:8]([CH3:7])[CH2:19][CH2:20][CH:21]=[C:22]([CH3:24])[CH3:23])[CH:29]([O:32][CH3:33])[O:30][CH3:31]

Participants

7

Reactant 4

HCID 962WaterHCID 20238235HCID 20238235, compoundHCID 23665647Potassium tert-butoxideHCID 73098283HCID 73098283, compound

Product 1

HCID 76044689HCID 76044689, compoundYield 65.7%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-27.5 °C

Procedure

To a 500 mL three-neck reaction flask protected from atmospheric moisture by nitrogen gas throughout the course of the reaction a solution of 2.4 g potassium t-butoxide (0.11 mol) in 60 mL of anhydrous tetrahydrofuran was added with an external cold bath to maintain the internal temperature of approximately −30 to −25° C. Then diethyl 3,7-dimethyl-2,6-octadiene-phosphonate (3B) (0.10 mol) was added dropwise over 30 min under mechanical stirring and the reaction mixture was subsequently stirred in the cold for 60 min to ensure the formation of carbanion thoroughly. Then 13.2 g of 2-methyl-3,3-dimethoxy-1-propanal (4A) (0.10 mol) was added dropwise at −30˜25° C. over 1 h and the reaction mixture was subsequently stirred for 30 min at this temperature until the reaction completed according to GC. Followed by the addition of 50 mL water and 100 mL ether and stirring for 10 min, after stratification, the organic layer was washed with 5% aqueous sodium chloride (3×25 mL), then dried over anhydrous magnesium sulfate and subsequently filtered. Removal of the volatile organic solvents in vacuo, the residue subsequently was fractional distillated to afford 17.9 g of (5-E and 5-Z)-2,6,10-trimethyl-1,1-dimethoxy-3,5,9-undecatriene (2C) of 99-103° C./1 mmHg, as a colorless liquid with GC content of 92.5% (total content of cis and trans) and the yield of 65.7%. There are 2 peaks according to GC and GC-MS. ascertained is the same with that of Example II

Workup

  1. additionwas added with an external cold bath
  2. stirringthe reaction mixture was subsequently stirred in the cold for 60 min
  3. stirringthe reaction mixture was subsequently stirred for 30 min at this temperature until the reaction
  4. stirringstirring for 10 min
  5. washafter stratification, the organic layer was washed with 5% aqueous sodium chloride (3×25 mL)
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationsubsequently filtered
  8. customRemoval of the volatile organic solvents in vacuo

Sources & evidence

ORD record
ord-c7f44a2f3c624afca214fc0548ae8bb2
Source dataset
uspto-grants-2015_06
Patent number
US09051254B2

Reaction notes

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