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Formic Acid → Methyl 2-azaadamantane-5-carboxylate

HRID 623981
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 623981
[CH:1]12[CH2:10][C:5]3(O)[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[NH:2]1)[CH2:8]2.[CH:12]([OH:14])=[O:13].OS(O)(=O)=O.O=S(=O)=O.[CH3:24]O>>[CH:1]12[CH2:10][C:5]3([C:12]([O:14][CH3:24])=[O:13])[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[NH:2]1)[CH2:8]2
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

5

Edukt 4

HCID 284Formic Acid2×HCID 887MethanolHCID 24681Fuming sulfuric acidHCID 89720338HCID 89720338, Verbindung

Produkt 1

HCID 74891108Methyl 2-azaadamantane-5-carboxylateAusbeute 50 %

Reaktionsbedingungen

Temperatur
60 °C

Versuchsvorschrift

To 2-azatricyclo[3.3.1.13,7]decan-5-ol (Intermediate-7) (1.5 g, 5.9 mmol, 1 eq), 98% formic acid (9 ml) was added drop wise with vigorous gas evolution for over 30 minutes to a rapidly stirred 30% oleum (36 ml) heated to 60° C. Upon completion of this addition, 99% formic acid (9 ml) was slowly added for the next 30 minutes. The reaction mixture was stirred for another 1 hr at 60° C. (monitored by LCMS). The reaction mixture thus formed was then slowly poured into vigorously stirred methanol (75 ml) cooled to 00° C. The mixture was allowed to slowly warm to room temperature while stirring the reaction mixture for 4-5 hrs. The mixture was then concentrated under vacuum. The residue was poured into ice (30 g) and basified with saturated Na2CO3 solution. The aqueous layer was extracted with 5% methanol in DCM (3×100 ml). Combined organic layer was washed with brine and dried over Na2SO4. The organic layer was finally concentrated to get intermediate-8, (550 mg, 50% yield) as an oily mass.

Aufarbeitung

  1. additionwas slowly added for the next 30 minutes
  2. customThe reaction mixture thus formed
  3. temperaturecooled to 00° C
  4. temperatureto slowly warm to room temperature
  5. stirringwhile stirring the reaction mixture for 4-5 hrs
  6. concentrationThe mixture was then concentrated under vacuum
  7. additionThe residue was poured into ice (30 g)
  8. extractionThe aqueous layer was extracted with 5% methanol in DCM (3×100 ml)
  9. washCombined organic layer was washed with brine
  10. dry with materialdried over Na2SO4
  11. concentrationThe organic layer was finally concentrated
  12. customto get intermediate-8

Quellen und Nachweise

ORD-Eintrag
ord-25e8b92db2bc4bee8b57c1a676c36855
Quelldatensatz
uspto-grants-2016_04
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US09303016B2

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