Hydrochloric Acid → HCID 15857586, compound

HRID 1384445Notes

Reaction equation

HRID 1384445 reaction equation
[CH3:1][C:2]1[CH:7]=[C:6]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][N:9]=2)[N:5]=[C:4]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][N:15]=2)[CH:3]=1.[Li+].CC([N-]C(C)C)C.Br[CH2:29][CH2:30][CH:31]1OCC[O:32]1.Cl.C([O-])(O)=O.[Na+]>C1COCC1.[Cl-].[Na+].O>[CH:31]([CH2:30][CH2:29][CH2:1][C:2]1[CH:7]=[C:6]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][N:9]=2)[N:5]=[C:4]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][N:15]=2)[CH:3]=1)=[O:32]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 877762-(2-Bromoethyl)-1,3-dioxolaneHCID 516892Sodium BicarbonateHCID 2724682Lithium diisopropylamideHCID 10944756HCID 10944756, compound

Product 1

HCID 15857586HCID 15857586, compoundYield 56%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
-78 °C

Procedure

a 100 mL three necked RB flask, equipped with a rubber septum, a teflon coated stir bar and a gas inlet adaptor was flushed with N2. 4′-methyl-2,2′:6′,2″-terpyridine (18) (0.494 gm., 2 mmol), prepared by literature methods (see K. T. Potts, et al, J. Am. Chem. Soc., 1987, 109, 3961-3967) was dissolved in dry THF (10 mL) and was syringed into the flask. The reaction mixture was cooled to −78° C. and LDA (1.6 mL, 2.4 mmol) was added via syringe. The resulting dark brown mixture was stirred for 2 hr. at −78° C. 2-(2-bromoethyl)-1,3-dioxolane (0.434 mL, 2.4 mmol) was syringed into the reaction mixture, stirred for 1 hr. at −78° C. and allowed to warm to room temperature overnight. The mixture was poured over 10 ml brine and the aqueous layer was extracted with CH2Cl2. The extracts were dried over MgSO4 and evaporated to dryness to yield the crude acetal. The acetal was hydrolyzed with 1M HCl (10 mL) by heating to 50-60° C. for 2 hours. The solution was then neutralized with aqueous NaHCO3 and extracted with CH2Cl2. The extracts were dried over MgSO4 and evaporated to dryness to yield the crude aldehyde. Purification by flash chromatography (neutral alumina, CH2Cl2 elution) gave pure aldehyde (19) (0.339 gm., 1.12 mmol, 56%).

Workup

  1. customwas flushed with N2
  2. customat −78° C
  3. stirringstirred for 1 hr
  4. customat −78° C.
  5. temperatureto warm to room temperature overnight
  6. extractionthe aqueous layer was extracted with CH2Cl2
  7. dry with materialThe extracts were dried over MgSO4
  8. customevaporated to dryness
  9. customto yield the crude acetal
  10. temperatureby heating to 50-60° C. for 2 hours
  11. extractionextracted with CH2Cl2
  12. dry with materialThe extracts were dried over MgSO4
  13. customevaporated to dryness
  14. customto yield the crude aldehyde
  15. customPurification
  16. washby flash chromatography (neutral alumina, CH2Cl2 elution)

Sources & evidence

ORD record
ord-c8fd1650a9094bd08041cc6b4c46294e
Source dataset
uspto-grants-2001_07
Patent number
US06258941B1

Reaction notes

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