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2-(Ethoxymethylene)propanedinitrile → 5-amino-1-cyclobutyl-1H-pyrazole-4-carbonitrile

HRID 1916245
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1916245
Cl.Cl.[CH:3]1([NH:7][NH2:8])[CH2:6][CH2:5][CH2:4]1.[O-]CC.[Na+].C(O[CH:16]=[C:17]([C:20]#[N:21])[C:18]#[N:19])C>CCO>[NH2:21][C:20]1[N:7]([CH:3]2[CH2:6][CH2:5][CH2:4]2)[N:8]=[CH:16][C:17]=1[C:18]#[N:19]
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

5

Edukt 3

HCID 671522-(Ethoxymethylene)propanedinitrileHCID 2723922Sodium ethoxideHCID 43423022Cyclobutylhydrazine dihydrochloride

Produkt 1

HCID 498535445-amino-1-cyclobutyl-1H-pyrazole-4-carbonitrile

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 702EthanolLösungsmittel2×

Versuchsvorschrift

A suspension of cyclobutylhydrazine dihydrochloride (11.63 g, 73.12 mmol) in EtOH (110 mL) was cooled in an ice bath and treated portion-wise with solid sodium ethoxide (9.95 g, 146 mmol) over 45 mins, while keeping the internal temp of the reaction mixture at approximately 0° C. The mixture was stirred in the ice bath for an additional hour, and then a solution of (ethoxymethylene)malononitrile (8.93 g, 73.1 mmol) in EtOH (70 mL) was added drop-wise over about 1.5 h, at a rate which maintained the internal temperature of the reaction mixture between 0° C. and 5° C. The reaction was then allowed to warm to room temp over about 18 h, after which it was heated at reflux for 1.5 h. After cooling to room temp, solvents were removed in vacuo, and the residue was partitioned between EtOAc and water. The aqueous layer was extracted twice with additional EtOAc, and the combined organic layers were washed with saturated aqueous sodium chloride solution, dried over sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure to provide crude C14, which was used in the next step without purification. Yield: 14.1 g, >100% mass recovery. 1H NMR (300 MHz, CDCl3) δ 1.9 (m, 2H), 2.4 (m, 2H), 2.65 (m, 2H), 4.25 (br s, 2H), 4.45 (m, 1H), 7.5 (s, 1H).

Aufarbeitung

  1. temperaturewas cooled in an ice bath
  2. customat approximately 0° C
  3. temperatureat a rate which maintained the internal temperature of the reaction mixture between 0° C. and 5° C
  4. temperatureafter which it was heated
  5. temperatureat reflux for 1.5 h
  6. temperatureAfter cooling to room temp
  7. customsolvents were removed in vacuo
  8. customthe residue was partitioned between EtOAc and water
  9. extractionThe aqueous layer was extracted twice with additional EtOAc
  10. washthe combined organic layers were washed with saturated aqueous sodium chloride solution
  11. dry with materialdried over sodium sulfate
  12. filtrationfiltered
  13. concentrationThe filtrate was concentrated under reduced pressure
  14. customto provide crude C14, which
  15. customwas used in the next step without purification

Quellen und Nachweise

ORD-Eintrag
ord-7483e3a2ca334781b6017af31b2fb710
Quelldatensatz
uspto-grants-2013_12
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08618117B2

Notizen zur Reaktion

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