Nicotinic Acid → Chloromethyl nicotinate

HRID 359896Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 359896
[C:1]([OH:9])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[N:4][CH:3]=1.C(=O)(O)[O-].[Na+].S(Cl)(O[CH2:19][Cl:20])(=O)=O>O.O1CCCC1.S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC>[C:1]([O:9][CH2:19][Cl:20])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[N:4][CH:3]=1

Komponenten

7

Edukt 3

HCID 938Nicotinic AcidHCID 516892Sodium BicarbonateHCID 2733556Chloromethyl chlorosulfate

Produkt 1

HCID 14608830Chloromethyl nicotinateAusbeute 74,8 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 94433Tetrabutylammonium hydrogen sulfateKatalysatorHCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

To a suspension of nicotinic acid (1.23 g, 0.01 mol) in a mixture of 10 mL of water and 20 mL of tetrahydrofuran were added tetrabutylammonium hydrogensulfate (0.34 g, 1 mmol) and sodium bicarbonate (3.19 g, 0.038 mol), with vigorous stirring. Chloromethyl chlorosulfate (1.81 g, 0.011 mol) in 5 mL of tetrahydrofuran was added dropwise, keeping the temperature below 30° C. The reaction mixture was stirred for 1 hour, then the layers were separated and the organic layer was dried by azeotroping with 1:1 acetonitrile/benzene. The residue was passed through a column of neutral alumina, eluting with chloroform. The chloroform layer was evaporated to give 1.28 g (74.8%) of an oily residue, which was confirmed by NMR analysis to have the structural formula: ##STR158##

Aufarbeitung

  1. customthe temperature below 30° C
  2. customthe layers were separated
  3. customthe organic layer was dried
  4. customby azeotroping with 1:1 acetonitrile/benzene
  5. washeluting with chloroform
  6. customThe chloroform layer was evaporated

Quellen und Nachweise

ORD-Eintrag
ord-df8f192939584372850112b274329d27
Quelldatensatz
uspto-grants-1991_03
Patentnummer
US05002935

Notizen zur Reaktion

Wird geladen…